WO2012116695A1 - Molybdenum and tungsten metal complexes and use thereof as precatalysts for olefin metathesis - Google Patents
Molybdenum and tungsten metal complexes and use thereof as precatalysts for olefin metathesis Download PDFInfo
- Publication number
- WO2012116695A1 WO2012116695A1 PCT/DE2012/100047 DE2012100047W WO2012116695A1 WO 2012116695 A1 WO2012116695 A1 WO 2012116695A1 DE 2012100047 W DE2012100047 W DE 2012100047W WO 2012116695 A1 WO2012116695 A1 WO 2012116695A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- halogen
- alkyloxy
- trifluoromethyl
- different
- Prior art date
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- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 239000012041 precatalyst Substances 0.000 title claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 20
- 229910052721 tungsten Inorganic materials 0.000 title claims description 20
- 239000011733 molybdenum Substances 0.000 title description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title description 15
- 239000010937 tungsten Substances 0.000 title description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- -1 C 1 -C 12 - Chemical group 0.000 claims description 78
- 125000003118 aryl group Chemical group 0.000 claims description 54
- 229910052736 halogen Inorganic materials 0.000 claims description 49
- 150000002367 halogens Chemical class 0.000 claims description 49
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 43
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 37
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000001424 substituent group Chemical group 0.000 claims description 26
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 17
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims 6
- 229910052702 rhenium Inorganic materials 0.000 abstract 1
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 238000005481 NMR spectroscopy Methods 0.000 description 34
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 21
- 125000001118 alkylidene group Chemical group 0.000 description 21
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 239000003446 ligand Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 150000005045 1,10-phenanthrolines Chemical class 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 3
- MLRRGHUJCYZIBG-UHFFFAOYSA-N (3,5-dimethyl-1h-pyrazol-4-yl)oxyboronic acid Chemical compound CC1=NNC(C)=C1OB(O)O MLRRGHUJCYZIBG-UHFFFAOYSA-N 0.000 description 2
- BYSUYBCCLCSGPR-UHFFFAOYSA-N 1h-pyrazol-5-yloxyboronic acid Chemical compound OB(O)OC1=CC=NN1 BYSUYBCCLCSGPR-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 239000001116 FEMA 4028 Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000037 tert-butyldiphenylsilyl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1[Si]([H])([*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IKPNXAIGJZHKQY-UHFFFAOYSA-N 2,2-dimethyl-6-phenyl-5,6-dihydrooxasiline Chemical compound C1C=C[Si](C)(C)OC1C1=CC=CC=C1 IKPNXAIGJZHKQY-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- WZVWSOXTTOJQQQ-UHFFFAOYSA-N 2-bromo-6-(6-bromopyridin-2-yl)pyridine Chemical group BrC1=CC=CC(C=2N=C(Br)C=CC=2)=N1 WZVWSOXTTOJQQQ-UHFFFAOYSA-N 0.000 description 1
- OHJPGUSXUGHOGE-UHFFFAOYSA-N 2-methyl-6-(6-methylpyridin-2-yl)pyridine Chemical group CC1=CC=CC(C=2N=C(C)C=CC=2)=N1 OHJPGUSXUGHOGE-UHFFFAOYSA-N 0.000 description 1
- LLCYXFYLGPOKQO-UHFFFAOYSA-N 2-methyl-6-pyridin-2-ylpyridine Chemical group CC1=CC=CC(C=2N=CC=CC=2)=N1 LLCYXFYLGPOKQO-UHFFFAOYSA-N 0.000 description 1
- XRIMFSNDQQKFRO-UHFFFAOYSA-N 2-pyridin-2-yl-4-pyrrolidin-1-ylquinoline Chemical compound C1CCCN1C1=CC(C=2N=CC=CC=2)=NC2=CC=CC=C12 XRIMFSNDQQKFRO-UHFFFAOYSA-N 0.000 description 1
- YQZGQXPHGLAEHA-UHFFFAOYSA-N 2-pyridin-2-ylquinoline Chemical compound N1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 YQZGQXPHGLAEHA-UHFFFAOYSA-N 0.000 description 1
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical compound C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 description 1
- NPAXPTHCUCUHPT-UHFFFAOYSA-N 3,4,7,8-tetramethyl-1,10-phenanthroline Chemical compound CC1=CN=C2C3=NC=C(C)C(C)=C3C=CC2=C1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 description 1
- GIEQBYJCGYHHSU-UHFFFAOYSA-N 4,7-dichloro-1,10-phenanthroline Chemical compound C1=CC2=C(Cl)C=CN=C2C2=C1C(Cl)=CC=N2 GIEQBYJCGYHHSU-UHFFFAOYSA-N 0.000 description 1
- ZPGVCQYKXIQWTP-UHFFFAOYSA-N 4,7-dimethoxy-1,10-phenanthroline Chemical compound C1=CC2=C(OC)C=CN=C2C2=C1C(OC)=CC=N2 ZPGVCQYKXIQWTP-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- FHGLROTYMYQNCC-UHFFFAOYSA-N 4-(2-pyridin-2-ylquinolin-4-yl)morpholine Chemical compound C1COCCN1C1=CC(C=2N=CC=CC=2)=NC2=CC=CC=C12 FHGLROTYMYQNCC-UHFFFAOYSA-N 0.000 description 1
- IMEVSAIFJKKDAP-UHFFFAOYSA-N 4-methoxy-2-(4-methoxypyridin-2-yl)pyridine Chemical compound COC1=CC=NC(C=2N=CC=C(OC)C=2)=C1 IMEVSAIFJKKDAP-UHFFFAOYSA-N 0.000 description 1
- NAZZKEZTSOOCSZ-UHFFFAOYSA-N 4-methyl-1,10-phenanthroline Chemical compound C1=CC2=CC=CN=C2C2=C1C(C)=CC=N2 NAZZKEZTSOOCSZ-UHFFFAOYSA-N 0.000 description 1
- NBPGPQJFYXNFKN-UHFFFAOYSA-N 4-methyl-2-(4-methylpyridin-2-yl)pyridine Chemical group CC1=CC=NC(C=2N=CC=C(C)C=2)=C1 NBPGPQJFYXNFKN-UHFFFAOYSA-N 0.000 description 1
- OXMSMRJQZMTIMT-UHFFFAOYSA-N 4-phenyl-2-(4-phenylpyridin-2-yl)pyridine Chemical group C1=CC=CC=C1C1=CC=NC(C=2N=CC=C(C=2)C=2C=CC=CC=2)=C1 OXMSMRJQZMTIMT-UHFFFAOYSA-N 0.000 description 1
- USOJNBCSEBSXNR-UHFFFAOYSA-N 4-piperidin-1-yl-2-pyridin-2-ylquinoline Chemical compound C1CCCCN1C1=CC(C=2N=CC=CC=2)=NC2=CC=CC=C12 USOJNBCSEBSXNR-UHFFFAOYSA-N 0.000 description 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical group CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 1
- BRPQDJPJBCQFSR-UHFFFAOYSA-N 5,6-dimethyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=C(C)C3=CC=CN=C3C2=N1 BRPQDJPJBCQFSR-UHFFFAOYSA-N 0.000 description 1
- XDUUQOQFSWSZSM-UHFFFAOYSA-N 5-chloro-1,10-phenanthroline Chemical compound C1=CC=C2C(Cl)=CC3=CC=CN=C3C2=N1 XDUUQOQFSWSZSM-UHFFFAOYSA-N 0.000 description 1
- UJAQYOZROIFQHO-UHFFFAOYSA-N 5-methyl-1,10-phenanthroline Chemical compound C1=CC=C2C(C)=CC3=CC=CN=C3C2=N1 UJAQYOZROIFQHO-UHFFFAOYSA-N 0.000 description 1
- PDDBTWXLNJNICS-UHFFFAOYSA-N 5-nitro-1,10-phenanthroline Chemical compound C1=CC=C2C([N+](=O)[O-])=CC3=CC=CN=C3C2=N1 PDDBTWXLNJNICS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PTRATZCAGVBFIQ-UHFFFAOYSA-N Abametapir Chemical group N1=CC(C)=CC=C1C1=CC=C(C)C=N1 PTRATZCAGVBFIQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- LYUUVYQGUMRKOV-UHFFFAOYSA-N Diethyl diallylmalonate Chemical compound CCOC(=O)C(CC=C)(CC=C)C(=O)OCC LYUUVYQGUMRKOV-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000000023 Kugelrohr distillation Methods 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- FYOKZZNUNQUQRW-UHFFFAOYSA-N diethyl 3,4-dimethylcyclopent-3-ene-1,1-dicarboxylate Chemical compound CCOC(=O)C1(C(=O)OCC)CC(C)=C(C)C1 FYOKZZNUNQUQRW-UHFFFAOYSA-N 0.000 description 1
- RIWCVIQHMHNTRG-UHFFFAOYSA-N diethyl 3-tert-butylcyclopent-3-ene-1,1-dicarboxylate Chemical compound CCOC(=O)C1(C(=O)OCC)CC=C(C(C)(C)C)C1 RIWCVIQHMHNTRG-UHFFFAOYSA-N 0.000 description 1
- AYKIAWRITOYVSR-UHFFFAOYSA-N diethyl cyclopent-3-ene-1,1-dicarboxylate Chemical compound CCOC(=O)C1(C(=O)OCC)CC=CC1 AYKIAWRITOYVSR-UHFFFAOYSA-N 0.000 description 1
- 125000004212 difluorophenyl group Chemical group 0.000 description 1
- 125000005805 dimethoxy phenyl group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- UERMJDAMIFUQEN-UHFFFAOYSA-N heptyl 2-(4-heptoxycarbonylquinolin-2-yl)quinoline-4-carboxylate Chemical compound C1=CC=CC2=NC(C=3C=C(C4=CC=CC=C4N=3)C(=O)OCCCCCCC)=CC(C(=O)OCCCCCCC)=C21 UERMJDAMIFUQEN-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000006303 iodophenyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UFLDXRGRABJXCI-UHFFFAOYSA-N tert-butyl-dimethyl-(2-methylcyclopent-2-en-1-yl)oxysilane Chemical compound CC1=CCCC1O[Si](C)(C)C(C)(C)C UFLDXRGRABJXCI-UHFFFAOYSA-N 0.000 description 1
- WQFQDHNJNBYWGU-JLHYYAGUSA-N tert-butyl-dimethyl-[(2e)-3-methylocta-2,7-dien-4-yl]oxysilane Chemical compound C=CCCC(C(/C)=C/C)O[Si](C)(C)C(C)(C)C WQFQDHNJNBYWGU-JLHYYAGUSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000165 tricyclic carbocycle group Chemical group 0.000 description 1
- 125000001680 trimethoxyphenyl group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/12—Nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/66—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
Definitions
- the present invention relates to metal complexes of molybdenum or tungsten, processes for their preparation and their use as precatalysts for olefin metathesis reactions.
- Alkene metathesis is understood as meaning the mutual transalkylidenation of alkenes according to Scheme 1 (Ivin, KJ, Mol, JC Olefin Metathesis and Metathesis Polymerization, Academic Press San Diego, 1997).
- Alkene metatheses are catalyzed by metal compounds which may be present in the reaction mixture in homogeneous or heterogeneous form.
- catalytically active species are so-called Schrock alkylidene, which can be prepared in situ or ex situ (Schröck, R. R. Chem. Rev. 2002, 102, 145).
- Schrock alkylidene derivatives of molybdenum and tungsten which are distinguished by high or very high catalytic activity, are frequently used (Schröck, RR, Chem. Rev. 2009, 109, 321 1, Schröck, RR, Hoveyda, AH Angew. Chem.
- Schrock alkylidenes of molybdenum and tungsten are also commercially available.
- Schrock alkylidenes of molybdenum and tungsten are typically very sensitive to air and moisture and therefore must be under inert conditions be handled and implemented. Air and moisture decompose them within a short time; In most cases, this decomposition occurs within a few seconds. Due to this high sensitivity, the use of Schrock alkylidenes of molybdenum and tungsten requires special working techniques and in some cases considerable apparatus and preparative effort.
- Schrock alkylidene of molybdenum and tungsten can be stabilized by adduct formation with donor ligands.
- donor ligands in the literature mostly ethers and phosphines were used, in some cases also nitrogen ligands such as pyridine, Pyridine derivatives or quinuclidine (Schröck, RR, Crowe, WE, Bazan, G.C .; DiMare, M., O'Regan, MB; Schofield, MH Organometallics 1991, 10, 1832); Ether adducts, however, remain very sensitive to air and moisture.
- the stability of the phosphane, quinuclidine or pyridine adducts depends on the donor strength and the size of the phosphines chosen, the quinuclidine or the pyridines chosen, as well as the electrophilicity of the Schrock alkylidene chosen. NMR measurements show that the complex formation is partially reversible even at room temperature in solution. In no case has been reported on the stability of the formed adducts to air and / or moisture.
- hydrotris (pyrazolyl) borate or hydrotris (3,5-dimethylpyrazolyl) borate By complexing Schröck alkylidenes with hydrotris (pyrazolyl) borate or hydrotris (3,5-dimethylpyrazolyl) borate, air-stable adducts can be prepared.
- a bipyridine adduct of a Schrock methylidene complex 1 was described as such (Fox, H.H., Lee, J.-K., Park, L.Y., Schröck, R.R. Organometallics
- the present invention accordingly provides metal complexes of the general formula I.
- M stands for Mo or W
- R is C1-C12 alkyl, 5- to 18-membered aryl, which in turn contains one or more identical or different C 1 -C 12 -alkyl, 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl ) may be substituted amino, halogen, trifluoromethyl, cyano, nitro radicals, the substituents X, Y may be the same or different and may be independently selected from: halogen, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, pyrrolyl, Ci-Ci2-alkyloxy 5- to 18-membered aryloxy, tri (C -C 2 alkyl) silyloxy, di (Ci-Ci 2 alkyl) (C 6 -C 8 aryl) silyl
- R 3 is Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn with one or more identical or different d-Ci 2 alkyl, 5- to 18-membered aryl, Ci-Ci 2 -Alkyloxy, di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
- R a , R b , R c , R d , R e , R f , R 9 , R h may be the same or different and may be selected independently from H, halogen, nitro, cyano, trifluoromethyl, d-Ci 2 - alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, Ci-Ci2 alkyloxy, di- (dC 4 - alkyl) amino, in turn, with one or more identical or different C 1 -C 12 - alkyl , 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) -amino, halogen, trifluoromethyl, cyano, nitro radicals, or the radicals R d and R e with formation a 5 to 8 membered ring are connected to each other,
- radicals R d and R e may also be linked together to form a 5- to 8-membered ring and together represent a radical R 48 , the CR 49 R 50 ,
- R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently selected and may have the same meaning as R a .
- the metal complexes of the formula I form stable compounds in air. It is believed that the stabilization occurs by complexation to suitable nitrogen ligands.
- Preferred compounds of the present invention are represented by the following formula 2,
- R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci 2- alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, C 1 -C 12 - alkyloxy, di- (C 1 -C 4 -alkyl) amino, which in turn with one or more identical or different Ci-Ci 2 Alkyl, 5- to 18-membered aryl, Ci-Ci 2 -alkyloxy, di- (Ci-C 4 - alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
- Ci-Ci 2 alkyl means a straight, branched or cyclic alkyl radical having 1 to 12 carbon atoms.
- 5- to 18-membered aryl means a mono-, bi- or tricyclic carbocyclic or heterocyclic aromatic radical which in turn may carry from 0 to 5 substituents selected from the list: Ci-Ci 2 -alkyl, Ci-C 2 alkoxy, di (C 1 -C 4 -alkyl) -amino, 5- to 18-membered aryl, halogen, cyano, nitro.
- Di- (C 1 -C 4 -alkyl) amino means an amino group having two identical or different straight-chain, branched or cyclic alkyl substituents each having 1 to 4 carbon atoms.
- Halogen in the context of the invention includes fluorine, chlorine, bromine and iodine.
- Preferred alkyl radicals in the context of this invention are straight-chain, branched or cyclic alkyl radicals having 1 to 12 carbon atoms. Preferred examples which may be mentioned are: methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, hexafluoroisopropyl, n-butyl, / 'so-butyl, sec-butyl, tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, Nonafluoro-ferf-butyl, 1-ethylpropyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, adamantyl.
- Preferred aryl radicals in the context of this invention are: phenyl, naphthyl, anthryl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, Isopropylphenyl, di (isopropyl) phenyl, tri (isopropyl) phenyl, tert-butylphenyl, di (tert-butyl) phenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, fluorophenyl, difluorophenyl, chlorophenyl, dichlorophenyl, bromophenyl, iodophenyl, pentafluorophenyl, dimethylaminophenyl, phenylphenyl, diphenylphenyl, (methoxy
- Preferred di- (C 1 -C 4 -alkyl) amino radicals in the context of this invention are the following C 1 -C 4 -alkylamino radicals: / V, / V-dimethylamino, / V, / V-diethylamino, / V-ethyl / V-methylamino , / V-Methyl- / Vn-propylamino, / V-isopropyl / Vn-propylamino, / V, / V-diisopropylamino, Nn-butyl / V-methylamino and / V-ferf-butyl / V-methylamino.
- the substituents R 2 , R 3 , R 4 may be identical or different and may be selected independently of one another from: H, halogen, trifluoromethyl, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R 23 may be identical or different and may be selected independently of one another from: H, methyl, trifluoromethyl, the substituents R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be the same or different and may be selected independently of one another from: H, C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -
- the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl
- the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R 23 may be the same or different and may be independently selected from: H, methyl, trifluoromethyl
- the substituents R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be the same or different and independently of one another can be selected from: H, C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -C 6 -alkyloxycarbonyl, phenyl, halogen, nitro.
- 1, 10-phenanthrolines which can be used in the context of this invention as ligands for stabilizing Schrock alkylidene complexes of molybdenum or tungsten are: 1, 10-phenanthroline, 4-methyl-1, 10-phenanthroline, 5 -Methyl-1,10-phenanthroline, 2,9-dimethyl [1,10] phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5-chloro [1,10] phenanthroline, 4,7-dichloro-1 , 10-phenanthroline, 4J-dichloro-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl [1,10] phenanthroline, 2,9-dimethyl-4 , 7-diphenyl [1, 10] phenanthroline, 5-nitro-1, 10-phenanthroline, 4,7-dimethoxy-1, 10-phenanthroline. Particularly preferred compounds in the context of the present
- R 25 , R 26 H, Me, CF 3
- R 1 , R 2 , R 3 and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R are as defined above,
- R 27 , R 28 , R 29 , R 30 , R 3 , R 32 , R 33 , R 34 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, ci C 12 -alkoxycarbonyl, C 1 -C 12 -alkyl, aryl 5- to 18-membered, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl ) -amino, which in turn contain one or more identical or different C 1 -C 12 -alkyl , 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) -amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, Likewise provided by the present invention are complexes of general formula 10, methods for their preparation, and their use as
- the substituents R 35 , R 36 , R 37 , R 38 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, C 1 -C 2 -alkyl, 5- to 18-membered aryl, C 2 Ci alkyloxy, di- (CC 4 alkyl) amino, tri (C -C 2 - alkyl) silyl, di (C -C 2 alkyl) (C 6 -C 8 aryl) silyl, (Ci-Ci 2 alkyl) di (C 6 -C 8 aryl) silyl, in turn, with one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, d-Ci2 alkyloxy, di- ( C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
- R 39 Me, phenyl.
- the substituent R can be selected from Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn by one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, Ci-Ci 2- alkyloxy, di- (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, the substituents X, Y may be the same or different and can be independently selected from: halogen, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, pyrrolyl, Ci-Ci2 alkyloxy, 5- to 18-membered aryloxy, tri (CrCl 2 - alkyl ) silyloxy, di (CrCl 2 alkyl) (C 6 -C 8 aryl) silyloxy, (Ci-C
- Preferred compounds in the context of the present invention are complexes of the general formula 18
- R 2 , R 3 , R 4 may be identical or different and may be selected independently of one another from: H, halogen, trifluoromethyl, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl,
- the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R May be the same or different and may be independently selected from: H, methyl, trifluoromethyl, the substituents R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and independently of one another can be selected from: H, C 1 -C 6 -alkyl, C 1 -C 6
- the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R May be the same or different and may be independently selected from: H, methyl, trifluoromethyl, the substituents R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and independently of one another can be selected from: H, Ci-C6-alkyl, C1-C6-
- 2,2'-bipyridines 2,2'-dipyridyls
- 2,2'-bipyridine 5,5'-dimethyl-2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 6,6'-dimethyl-2 , 2'-dipyridyl, 4-4'-dimethoxy-2-2'-bipyridine, 2,2'-biquinoline, 4,4'-di-tert-butyl-2,2'-dipyridyl, 2,2'-di-tert-butyl-2,2'-bipyridyl Bipyridinyl-4,4'-dicarboxylic acid dimethyl ester, 4,4'-diphenyl-2,2'-dipyridyl, 6,6'-dibromo
- R 25 , R 26 H, Me, CF 3
- Z methyl, iso-propyl, halogen.
- R 1 , R 2 and R 3 and R 35 , R 36 , R 37 , R 38 , R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are as defined above ,
- R 39 Me, phenyl.
- Another object of the present invention is a process for the preparation of the compounds of general formulas I.
- R a , R b , R c , R d , R e , R f , R 9 , R h are as defined above,
- a subject of the present invention is a process for the use of the complexes of the formulas I, 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 , 31, 38, 40, 42, 43 as precatalysts for carrying out alkene metathesis reactions by activation with a suitable additive
- a solution or a suspension of compound of the formulas I, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 38, 40, 42, 43 are reacted in a suitable solvent with anhydrous metal salts or metal complexes as additives, which in turn form stable 1, 10-phenanthroline complexes or 2,2'-Bipyridinkomplexe ,
- This activation takes place by decomplexation of the respective 1, 10-phenanthroline or
- Suitable for this activation are all anhydrous metal salts or metal complexes which form stable 1, 10 phenanthroline complexes or 2,2'-bipyridine complexes. Particularly preferred examples are mentioned in Scheme 3 and in the section "Examples”.
- Particularly preferred additives are: MgCl 2 , MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , Mnl 2 , FeCl 3 , AICl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znl 2 , Zn (triflate) 2 , Zn (trifluoroacetate 2 .
- the activation can be carried out at different temperatures, preferably at temperatures between -20 ° C and + 140 ° C, more preferably at temperatures between 20 ° C and 1 10 ° C.
- Suitable solvents are all solvents which do not lead to the decomposition of the liberated Schrock alkylidene complexes of molybdenum or tungsten; preferred solvents are hydrocarbons, halohydrocarbons and ethers; Particularly preferred are pentanes, hexanes, heptanes, octanes, petroleum ethers, benzene, toluene, xylenes, cumene, decalin, chlorobenzene, bromobenzene, fluorobenzene, trifluoromethylbenzene, dichlorobenzenes, trichlorobenzenes, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, t
- phen 1, 10-phenanthroline
- bipy 2,2'-bipyridine
- dme 1, 2-dimethoxyethane
- biphene biphenyl-2,2'-diolate
- TMS trimethylsilyl
- TBS tert-butyldimethylsilyl
- TBDPS tert-butyldiphenylsilyl.
- the 2,2'-bipyridine derivatives used to prepare the complexes were dissolved in toluene and the solution was dried over molecular sieve 5A (MS 5A). Subsequently, the molecular sieve was filtered off, the filtrate was concentrated and the remaining 2,2'-bipyridine derivative stored under argon.
- the 1, 10-phenanthroline derivatives used to prepare the complexes were either purified by double sublimation under high vacuum and dried, or dissolved in toluene and the solution dried over molecular sieves 5A (MS 5A); then the toluene was distilled off in vacuo and the remaining 1, 10-phenanthroline derivative stored under argon.
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Abstract
The invention relates to metal complexes of general formula (I) and to a method for the production thereof, in which M, R1, R2, R3, X and Y in addition to Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh can have the meanings defined in the claims. Said metal complexes form air-stable compounds and are suitable as precatalysts in the olefin metathesis.
Description
Metallkomplexe des Molybdäns und Wolframs und ihre Verwendung als Metal complexes of molybdenum and tungsten and their use as
Präkatalysatoren für die Olefinmetathese Precatalysts for olefin metathesis
Die vorliegende Erfindung betrifft Metallkomplexe des Molybdäns oder Wolframs, Verfahren zu ihrer Herstellung und ihre Verwendung als Präkatalysatoren für Olefinmetathese-Reaktionen. The present invention relates to metal complexes of molybdenum or tungsten, processes for their preparation and their use as precatalysts for olefin metathesis reactions.
Unter Alkenmetathese versteht man die wechselseitige Umalkylidenierung von Alkenen gemäß Schema 1 (Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization, Academic Press San Diego, 1997).
Alkene metathesis is understood as meaning the mutual transalkylidenation of alkenes according to Scheme 1 (Ivin, KJ, Mol, JC Olefin Metathesis and Metathesis Polymerization, Academic Press San Diego, 1997).
Schema 1. Allgemeines Prinzip der Alkenmetathese Scheme 1. General principle of alkene metathesis
Alkenmetathesen werden durch Metallverbindungen katalysiert, die im Reaktionsgemisch in homogener oder heterogener Form vorliegen können. Als eigentlich katalytisch aktive Spezies gelten sogenannte Schrock-Alkylidene, die in situ oder ex situ dargestellt werden können (Schröck, R. R. Chem. Rev. 2002, 102, 145). Neben Alkylidenkomplexen des Rutheniums werden häufig Schrock-Alkylidene des Molybdäns und Wolframs benutzt, die sich durch hohe oder sehr hohe katalytische Aktivität auszeichnen (Schröck, R. R., Chem. Rev. 2009, 109, 321 1 ; Schröck, R. R.; Hoveyda, A. H. Angew. Chem. Int. Ed. 2003, 42, 4592); einige Schrock-Alkylidene des Molybdäns und Wolframs sind auch kommerziell erhältlich. Im Gegensatz zu Ruthenium-Alkylidenen (Vougioukalakis, G. C; Grubbs, R. R. Chem. Rev. 2010, 110, 1746) sind Schrock-Alkylidene des Molybdäns und Wolframs jedoch in der Regel sehr empfindlich gegenüber Luft und Feuchtigkeit und müssen daher unter inerten Bedingungen gehandhabt und umgesetzt werden. Durch Luft und Feuchtigkeit werden sie innerhalb kurzer Zeit zersetzt; in den meisten Fällen tritt diese Zersetzung innerhalb weniger Sekunden ein. Auf Grund dieser hohen Empfindlichkeit erfordert der Einsatz von Schrock-Alkylidenen des Molybdäns und Wolframs spezielle Arbeitstechniken sowie einen zum Teil erheblichen apparativen und präparativen Aufwand. Alkene metatheses are catalyzed by metal compounds which may be present in the reaction mixture in homogeneous or heterogeneous form. Actually catalytically active species are so-called Schrock alkylidene, which can be prepared in situ or ex situ (Schröck, R. R. Chem. Rev. 2002, 102, 145). In addition to ruthenium-containing alkylidene complexes, Schrock alkylidene derivatives of molybdenum and tungsten, which are distinguished by high or very high catalytic activity, are frequently used (Schröck, RR, Chem. Rev. 2009, 109, 321 1, Schröck, RR, Hoveyda, AH Angew. Chem. Int Ed 2003, 42, 4592); Some Schrock alkylidenes of molybdenum and tungsten are also commercially available. However, unlike ruthenium alkylidenes (Vougioukalakis, G.C., Grubbs, RR Chem. Rev. 2010, 110, 1746), Schrock alkylidenes of molybdenum and tungsten are typically very sensitive to air and moisture and therefore must be under inert conditions be handled and implemented. Air and moisture decompose them within a short time; In most cases, this decomposition occurs within a few seconds. Due to this high sensitivity, the use of Schrock alkylidenes of molybdenum and tungsten requires special working techniques and in some cases considerable apparatus and preparative effort.
Schrock-Alkylidene des Molybdäns und Wolframs können durch Adduktbildung mit Donorliganden stabilisiert werden. Als Donorliganden wurden in der Literatur meist Ether und Phosphane eingesetzt, in einigen Fällen auch Stickstoffliganden wie Pyridin,
Pyridinderivate oder Chinuclidin (Schröck, R. R., Crowe, W. E.; Bazan, G. C; DiMare, M.; O'Regan, M. B.; Schofield, M. H. Organometallics 1991 , 10, 1832); Ether-Addukte bleiben jedoch sehr luft- und feuchtigkeits-empfindlich. Die Stabilität der Phosphan-, Chinuclidin- oder Pyridinaddukte ist von der Donorstärke und der Größe der gewählten Phosphane, des Chinuclidins oder der gewählten Pyridine sowie von der Elektrophilie des gewählten Schrock-Alkylidenes abhängig. NMR Messungen zeigen, dass die Komplexbildung bereits bei Raumtemperatur in Lösung teilweise reversibel ist. In keinem Fall wurde über die Stabilität der gebildeten Addukte gegenüber Luft und/oder Feuchtigkeit berichtet. Durch Komplexierung von Schröck Alkylidenen mit Hydrotris(pyrazolyl)borat oder Hydrotris(3,5-dimethylpyrazolyl)borat lassen sich hingegen luftstabile Addukte herstellen. Allerdings kann weder Hydrotris(pyrazolyl)borat noch Hydrotris(3,5- dimethylpyrazolyl)borat durch Zugabe von Lewis-Säuren wie zum Beispiel AICI3 von diesen Addukten abgelöst werden, sodass sich der ursprüngliche Schröck Alkyliden- Komplex nicht wieder freisetzen lässt. Vielmehr führt die Zugabe von Lewis-Säuren wie zum Beispiel AICI3 zur Reaktion mit anderen Liganden des gebildeten Addukts und damit zur Bildung von einem oder mehreren neuen, strukturell nicht vollständig aufgeklärten Verbindungen (J. M. Boncella et al., J. Am. Chem. Soc. 1991 , 1 13, 7066; OrganometallicsSchrock alkylidene of molybdenum and tungsten can be stabilized by adduct formation with donor ligands. As donor ligands in the literature mostly ethers and phosphines were used, in some cases also nitrogen ligands such as pyridine, Pyridine derivatives or quinuclidine (Schröck, RR, Crowe, WE, Bazan, G.C .; DiMare, M., O'Regan, MB; Schofield, MH Organometallics 1991, 10, 1832); Ether adducts, however, remain very sensitive to air and moisture. The stability of the phosphane, quinuclidine or pyridine adducts depends on the donor strength and the size of the phosphines chosen, the quinuclidine or the pyridines chosen, as well as the electrophilicity of the Schrock alkylidene chosen. NMR measurements show that the complex formation is partially reversible even at room temperature in solution. In no case has been reported on the stability of the formed adducts to air and / or moisture. By complexing Schröck alkylidenes with hydrotris (pyrazolyl) borate or hydrotris (3,5-dimethylpyrazolyl) borate, air-stable adducts can be prepared. However, neither hydrotris (pyrazolyl) borate nor hydrotris (3,5-dimethylpyrazolyl) borate can be removed from these adducts by the addition of Lewis acids such as AICI 3 , so that the original Schröck alkylidene complex can not be released again. Rather, the addition of Lewis acids such as AICI 3 leads to the reaction with other ligands of the adduct formed and thus to the formation of one or more new, structurally not completely enlightened compounds (Bonmella JM et al., J. Am. Chem. Soc 1991, 1 13, 7066; Organometallics
1992, 11, 2342; Organometallics 1993, 12, 2814; J. Organomet. Chem. 1995, 485, 37). 1992, 11, 2342; Organometallics 1993, 12, 2814; J. Organomet. Chem. 1995, 485, 37).
In einem Fall wurde ein Bipyridin-Addukt eines Schrock-Methyliden-Komplexes 1 als solches beschrieben (Fox, H. H.; Lee, J.-K.; Park, L. Y.; Schröck, R. R. OrganometallicsIn one case, a bipyridine adduct of a Schrock methylidene complex 1 was described as such (Fox, H.H., Lee, J.-K., Park, L.Y., Schröck, R.R. Organometallics
1993, 12, 759) bei dem die Alkylideneinheit terminal, d. h. nicht weiter substituiert ist. Eine weitere Umsetzung des Methyliden-Komplexes 1 wurde nicht beschrieben. 1993, 12, 759) in which the alkylidene unit is terminal, d. H. not further substituted. Further implementation of the methylidene complex 1 has not been described.
Überraschenderweise hat sich nun herausgestellt, dass sich Schrock-Alkylidene des Molybdäns und Wolframs mit nicht-terminaler Alkylideneinheit durch Komplexierung (Adduktbildung) mit bidentaten Stickstoffliganden, wie zum Beispiel 1 ,10-Phenathrolin oder 2,2'-Bipyridin (2,2'-Dipyridyl) bzw. deren Derivaten soweit stabilisieren lassen, dass sie ohne besondere Vorsichtsmaßnahmen an der Luft gehandhabt und über lange Zeit
ohne besondere Vorkehrungen bei Raumtemperatur an Luft gelagert werden können, ohne dass Zersetzung eintritt. In einigen Fällen sind diese Addukte an der Luft bei Raumtemperatur über Monate lagerbar, ohne das Zersetzung eintritt. Allerdings weisen diese Komplexe selbst unter den bei Metathesereaktionen üblichen Reaktionsbedingungen keine nennenswerte katalytische Aktivität auf. Im Gegensatz zum bisherigen Stand des Wissens wurde jedoch überraschend gefunden, dass aus den genannten, aus Schrock-Alkylidenen des Molybdäns und Wolframs und bidentaten Stickstoffliganden hergestellten Komplexen (Addukten) mit Hilfe geeigneter Additiva in einem inerten Lösungsmittel die katalytisch aktiven Schrock-Alkylidene unverändert und in guten Ausbeuten wieder freigesetzt werden können; dadurch wird deren hohe katalytische Aktivität wiederhergestellt. Das in dieser Erfindung beschriebene Vorgehen zur Darstellung und Nutzung luftstabiler Addukte und der Freisetzung der aktiven Spezies durch Reaktion dieser Addukte mit geeigneten Additiva vereinfacht die Handhabung und Nutzung von Schrock-Alkylidene des Molybdäns und Wolframs erheblich, da weder spezielle Arbeitstechniken noch ein besonderer apparativer Aufwand nötig sind. Surprisingly, it has now been found that Schrock alkylidene of molybdenum and tungsten having non-terminal alkylidene unit by complexation (adduct formation) with bidentate nitrogen ligands, such as 1, 10-phenathroline or 2,2'-bipyridine (2,2'- Dipyridyl) or their derivatives stabilize so far that they are handled without special precautions in the air and over a long time can be stored at room temperature without special precautions in air, without decomposition occurs. In some cases, these adducts can be stored in air at room temperature for months without decomposition. However, these complexes have no appreciable catalytic activity even under the reaction conditions customary in metathesis reactions. In contrast to the previous state of knowledge, however, it was surprisingly found that the catalytically active Schrock alkylidenes from the mentioned, prepared from Schrock alkylidenes of molybdenum and tungsten and bidentate nitrogen ligands complexes (adducts) with the aid of suitable additives in an inert solvent unchanged and in good yields can be released again; This restores their high catalytic activity. The procedure described in this invention for the preparation and use of air-stable adducts and the release of the active species by reaction of these adducts with suitable additives simplifies the handling and use of Schrock alkylidenes of molybdenum and tungsten considerably, since neither special techniques nor a special equipment required are.
Gegenstand der vorliegenden Erfindung sind demnach Metallkomplexe der allgemeinen Formel I The present invention accordingly provides metal complexes of the general formula I.
in der in the
M für Mo oder W steht, M stands for Mo or W,
R für C1-C12 Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen CrCi2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di- (Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, die Substituenten X, Y gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: Halogen, Methansulfonyloxy, Trifluormethansulfonyloxy, Benzolsulfonyloxy, Toluolsulfonyloxy, Pyrrolyl, Ci-Ci2-Alkyloxy, 5- bis 18-gliedriges Aryloxy, Tri(C Ci2-Alkyl)silyloxy, Di(Ci-Ci2-Alkyl)(C6-Ci8-Aryl)silyloxy, (Ci-Ci2-Alkyl)di(C6- Ci8-Aryl)silyloxy, Tris(Ci-Ci2-Alkyloxy)silyloxy, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkoxy, Di-(d- C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können,
R2 für H, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen CrCi2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di- (CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, stehen, R is C1-C12 alkyl, 5- to 18-membered aryl, which in turn contains one or more identical or different C 1 -C 12 -alkyl, 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl ) may be substituted amino, halogen, trifluoromethyl, cyano, nitro radicals, the substituents X, Y may be the same or different and may be independently selected from: halogen, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, pyrrolyl, Ci-Ci2-alkyloxy 5- to 18-membered aryloxy, tri (C -C 2 alkyl) silyloxy, di (Ci-Ci 2 alkyl) (C 6 -C 8 aryl) silyloxy, (Ci-Ci2 alkyl) di (C 6 -Ci8-aryl) silyloxy, tris (Ci-Ci2-alkyloxy) silyloxy, which in turn with one or more identical or different Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkoxy, di- ( C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals can be substituted, R 2 is H, Ci-Ci 2 alkyl, 5- to 18-membered aryl, which in turn with one or more identical or different CrCi 2 alkyl, 5- to 18-membered aryl, Ci-Ci 2 -Alkyloxy, di - (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
R3 für Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen d-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di- (Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, stehen, R 3 is Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn with one or more identical or different d-Ci 2 alkyl, 5- to 18-membered aryl, Ci-Ci 2 -Alkyloxy, di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
Ra, Rb, Rc, Rd, Re, Rf, R9, Rh gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus H, Halogen, Nitro, Cyano, Trifluormethyl, d- Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(d-C4- Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen C1-C12- Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, oder die Reste Rd und Re unter Bildung eines 5 bis 8 gliedrigen Ringes mit einander verbunden sind, R a , R b , R c , R d , R e , R f , R 9 , R h may be the same or different and may be selected independently from H, halogen, nitro, cyano, trifluoromethyl, d-Ci 2 - alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, Ci-Ci2 alkyloxy, di- (dC 4 - alkyl) amino, in turn, with one or more identical or different C 1 -C 12 - alkyl , 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) -amino, halogen, trifluoromethyl, cyano, nitro radicals, or the radicals R d and R e with formation a 5 to 8 membered ring are connected to each other,
Die Reste Rd und Re können auch unter Bildung eines 5 bis 8 gliedrigen Ringes mit einander verbunden sein und gemeinsam für einen Rest R48 stehen, der CR49R50,
The radicals R d and R e may also be linked together to form a 5- to 8-membered ring and together represent a radical R 48 , the CR 49 R 50 ,
CR69R70-CR7 R72-CR73R74-CR75CR76, CR77=CR78-CR79R80-CR8 CR82 und/oder CR83R84- C R85=CR87.C R88C R89 bedeutet jn we|chen R49, R50, R5 , R52, R53, R54, R55, R56, R57, R58,CR 69 R 70 -CR 7 R 72 -CR 73 R 74 -CR 75 CR 76 , CR 77 = CR 78 -CR 79 R 80 -CR 8 CR 82 and / or CR 83 R 84 - CR 85 = CR 87. CR 88 CR 89 means we | c hen R 49, R 50, R 5, R 52, R 53, R 54, R 55, R 56, R 57, R 58,
R59 R60 R61 R62 R63 R64 R65 R66 R67 R68 R69 R70 R71 R72 R73 R74 R75 R76 R77 R78 R 59 R 60 R 61 R 62 R 63 R 64 R 65 R 66 R 67 R 68 R 69 R 70 R 71 R 72 R 73 R 74 R 75 R 76 R 77 R 78
R79, R80, R81 , R82, R83, R84, R85, R86, R87, R88 und R89 jeweils unabhängig von einander ausgewählt sind und die gleiche Bedeutung haben können wie Ra. R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently selected and may have the same meaning as R a .
Die Metallkomplexe mit der Formel I bilden an Luft stabile Verbindungen. Es wird vermutet, dass die Stabilisierung durch Komplexierung an geeignete Stickstoffliganden erfolgt. The metal complexes of the formula I form stable compounds in air. It is believed that the stabilization occurs by complexation to suitable nitrogen ligands.
Bevorzugte Verbindungen der vorliegenden Erfindung sind durch folgende Formel 2 wiedergegeben, Preferred compounds of the present invention are represented by the following formula 2,
M, R , R2, R3, X und Y wie oben definiert sind, M, R, R 2 , R 3 , X and Y are as defined above,
die Substituenten R4, R5, R6, R7, R8, R9, R 0, R gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12- Alkyloxy, Di-(CrC4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(Ci-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. the substituents R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci 2- alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, C 1 -C 12 - alkyloxy, di- (C 1 -C 4 -alkyl) amino, which in turn with one or more identical or different Ci-Ci 2 Alkyl, 5- to 18-membered aryl, Ci-Ci 2 -alkyloxy, di- (Ci-C 4 - alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
Im Rahmen der vorliegenden Erfindung bedeuten: In the context of the present invention mean:
„Ci-Ci2-Alkyl" einen geradkettigen, verzweigten oder cyclischen Alkylrest mit 1 bis 12 Kohlenstoffatomen. "Ci-Ci 2 alkyl" means a straight, branched or cyclic alkyl radical having 1 to 12 carbon atoms.
„5- bis 18-gliedriges Aryl" einen mono-, bi- oder tricyclischen carbocyclischen oder heterocyclischen aromatischen Rest, der seinerseits 0 bis 5 Substituenten tragen kann aus der Liste: Ci-Ci2-Alkyl, Ci-Ci2-Alkoxy, Di(Ci-C4-Alkyl)amino, 5- bis 18-gliedriges Aryl, Halogen, Cyano, Nitro. "5- to 18-membered aryl" means a mono-, bi- or tricyclic carbocyclic or heterocyclic aromatic radical which in turn may carry from 0 to 5 substituents selected from the list: Ci-Ci 2 -alkyl, Ci-C 2 alkoxy, di (C 1 -C 4 -alkyl) -amino, 5- to 18-membered aryl, halogen, cyano, nitro.
„Di-(CrC4-Alkyl)amino" eine Amino-Gruppe mit zwei gleichen oder verschiedenen geradkettigen, verzweigten oder cyclischen Alkylsubstituenten, die jeweils 1 bis 4 Kohlenstoffatome aufweisen. "Di- (C 1 -C 4 -alkyl) amino" means an amino group having two identical or different straight-chain, branched or cyclic alkyl substituents each having 1 to 4 carbon atoms.
„Halogen" schließt im Rahmen der Erfindung Fluor, Chlor, Brom und lod ein. "Halogen" in the context of the invention includes fluorine, chlorine, bromine and iodine.
Bevorzugte Alkylreste im Rahmen dieser Erfindung sind geradkettige, verzweigte oder cyclische Alkylreste mit 1 bis 12 Kohlenstoffatomen. Beispielhaft und vorzugsweise seien genannt: Methyl, Trifluormethyl, Ethyl, n-Propyl, Isopropyl, Hexafluorisopropyl, n-Butyl, /'so-Butyl, sec-Butyl, ferf-Butyl, Trifluor-ferf-butyl, Hexafluor-ferf-butyl, Nonafluor-ferf-butyl, 1 -Ethylpropyl, n-Pentyl, n-Hexyl, Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl und Cycloheptyl, Adamantyl. Bevorzugte Arylreste im Rahmen dieser Erfindung sind: Phenyl, Naphthyl, Anthryl, Methylphenyl, Dimethylphenyl, Trimethylphenyl, Ethylphenyl, Diethylphenyl,
Isopropylphenyl, Di(isopropyl)phenyl, Tri(isopropyl)phenyl, tert-Butylphenyl, Di(tert- butyl)phenyl, Methoxyphenyl, Dimethoxyphenyl, Trimethoxyphenyl, Trifluormethylphenyl, Bis(trifluormethyl)phenyl, Fluorphenyl, Difluorphenyl, Chlorphenyl, Dichlorphenyl, Bromphenyl, lodphenyl, Pentafluorphenyl, Dimethylaminophenyl, Phenylphenyl, Diphenylphenyl, (Methoxycarbonyl)phenyl, (Ethoxycarbonyl)phenyl, (tert- Butoxycarbonyl)phenyl; ebenso bevorzugt sind heterocyclische Arylreste mit bis zu zwei Heteroatomen aus der Reihe N, O und/oder S wie beispielsweise Furyl, Thienyl, Thiazolyl, Oxazolyl, Indolyl, Isothiazolyl, Isoxazolyl, Pyrazolyl, Imidazolyl, Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, Benzofuranyl, Benzothiophenyl, Benzimidazolyl, Carbazolyl. Preferred alkyl radicals in the context of this invention are straight-chain, branched or cyclic alkyl radicals having 1 to 12 carbon atoms. Preferred examples which may be mentioned are: methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, hexafluoroisopropyl, n-butyl, / 'so-butyl, sec-butyl, tert-butyl, trifluoro-tert-butyl, hexafluoro-tert-butyl, Nonafluoro-ferf-butyl, 1-ethylpropyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, adamantyl. Preferred aryl radicals in the context of this invention are: phenyl, naphthyl, anthryl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, Isopropylphenyl, di (isopropyl) phenyl, tri (isopropyl) phenyl, tert-butylphenyl, di (tert-butyl) phenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, fluorophenyl, difluorophenyl, chlorophenyl, dichlorophenyl, bromophenyl, iodophenyl, pentafluorophenyl, dimethylaminophenyl, phenylphenyl, diphenylphenyl, (methoxycarbonyl) phenyl, (ethoxycarbonyl) phenyl, (tert-butoxycarbonyl) phenyl; also preferred are heterocyclic aryl radicals having up to two heteroatoms from the series N, O and / or S such as furyl, thienyl, thiazolyl, oxazolyl, indolyl, isothiazolyl, isoxazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, benzofuranyl, Benzothiophenyl, benzimidazolyl, carbazolyl.
Bevorzugte Di-(Ci-C4-Alkyl)amino Reste im Rahmen dieser Erfindung sind folgende Di- CrC4-Alkylamino Reste: /V,/V-Dimethylamino, /V,/V-Diethylamino, /V-Ethyl-/V-methylamino, /V-Methyl-/V-n-propylamino, /V-lsopropyl-/V-n-propylamino, /V,/V-Diisopropylamino, N-n- Butyl-/V-methylamino und /V-ferf-Butyl-/V-methylamino. Preferred di- (C 1 -C 4 -alkyl) amino radicals in the context of this invention are the following C 1 -C 4 -alkylamino radicals: / V, / V-dimethylamino, / V, / V-diethylamino, / V-ethyl / V-methylamino , / V-Methyl- / Vn-propylamino, / V-isopropyl / Vn-propylamino, / V, / V-diisopropylamino, Nn-butyl / V-methylamino and / V-ferf-butyl / V-methylamino.
Weiterhin bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemei Further preferred compounds in the context of the present invention are complexes of the general
M = Mo, W, M = Mo, W,
die Substituenten R 2, R 3, R 4 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Trifluormethyl, Methyl, Ethyl, Propyl, Butyl, iso-Propyl, tert-Butyl, die Substituenten R 5, R 6, R 7 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Ethyl, Propyl, Phenyl,
die Substituenten R 8, R 9, R20, R2 , R22, R23 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Trifluormethyl, die Substituenten R4, R5, R6, R7, R8, R9, R 0, R gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Ci-C6-Alkyl, Ci-C6-Alkyloxy, CrC6-Alkyloxycarbonyl, Phenyl, Halogen, Nitro. the substituents R 2 , R 3 , R 4 may be identical or different and may be selected independently of one another from: H, halogen, trifluoromethyl, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R 23 may be identical or different and may be selected independently of one another from: H, methyl, trifluoromethyl, the substituents R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be the same or different and may be selected independently of one another from: H, C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -C 6 -alkyloxycarbonyl, phenyl, halogen, nitro.
Ebenfalls bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formel 4 Also preferred compounds in the context of the present invention are complexes of the general formula 4
worin wherein
M = Mo, M = Mo,
die Substituenten R 5, R 6, R 7 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Ethyl, Propyl, Phenyl, die Substituenten R 8, R 9, R20, R2 , R22, R23 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Trifluormethyl, die Substituenten R4, R5, R6, R7, R8, R9, R 0, R gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Ci-C6-Alkyl, Ci-C6-Alkyloxy, CrC6-Alkyloxycarbonyl, Phenyl, Halogen, Nitro. the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R 23 may be the same or different and may be independently selected from: H, methyl, trifluoromethyl, the substituents R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be the same or different and independently of one another can be selected from: H, C 1 -C 6 -alkyl, C 1 -C 6 -alkyloxy, C 1 -C 6 -alkyloxycarbonyl, phenyl, halogen, nitro.
Beispiele für bevorzugte 1 ,10-Phenanthroline, die im Rahmen dieser Erfindung als Liganden zur Stabilisierung von Schrock-Alkyliden Komplexen des Molybdäns oder Wolframs eingesetzt werden können, sind: 1 , 10-Phenanthrolin, 4-Methyl-1 , 10- phenanthrolin, 5-Methyl-1 , 10-phenanthrolin, 2,9-Dimethyl[1 , 10]phenanthrolin, 5,6- Dimethyl-1 , 10-phenanthrolin, 5-Chlor[1 ,10]phenanthrolin, 4,7-Dichloro-1 , 10-phenanthrolin, 4J-Dichlor-1 , 10-phenanthrolin, 3,4,7, 8-Tetramethyl-1 ,10-phenanthrolin, 4,7- Diphenyl[1 , 10]phenanthrolin, 2,9-Dimethyl-4,7-diphenyl[1 ,10]phenanthrolin, 5-Nitro-1 , 10- phenanthrolin, 4,7-Dimethoxy-1 , 10-phenanthrolin.
Besonders bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formel 5-8 Examples of preferred 1, 10-phenanthrolines which can be used in the context of this invention as ligands for stabilizing Schrock alkylidene complexes of molybdenum or tungsten are: 1, 10-phenanthroline, 4-methyl-1, 10-phenanthroline, 5 -Methyl-1,10-phenanthroline, 2,9-dimethyl [1,10] phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 5-chloro [1,10] phenanthroline, 4,7-dichloro-1 , 10-phenanthroline, 4J-dichloro-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 4,7-diphenyl [1,10] phenanthroline, 2,9-dimethyl-4 , 7-diphenyl [1, 10] phenanthroline, 5-nitro-1, 10-phenanthroline, 4,7-dimethoxy-1, 10-phenanthroline. Particularly preferred compounds in the context of the present invention are complexes of the general formula 5-8
R24 = Me, Ph R 24 = Me, Ph
R25, R26 = H , Me, CF3 R 25 , R 26 = H, Me, CF 3
Z = Methyl, iso-Propyl, Halogen Z = methyl, iso-propyl, halogen
Ebenso sind Gegenstand der vorliegenden Erfindung Komplexe der allgemeinen Formel 9, Methoden zu deren Herstellung, sowie ihre Anwendung als Präkatalysatoren für die Alkenmetathese, Likewise provided by the present invention are complexes of general formula 9, methods for their preparation, and their use as precatalysts for alkene metathesis,
worin wherein
M, R1 , R2, R3 und R4, R5, R6, R7, R8, R9, R 0, R wie oben definiert sind, M, R 1 , R 2 , R 3 and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R are as defined above,
die Substitutenten R27, R28, R29, R30, R3 , R32, R33, R34 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(d-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können,
Ebenso sind Gegenstand der vorliegenden Erfindung Komplexe der allgemeinen Formel 10, Methoden zu deren Herstellung, sowie ihre Anwendung als Präkatalysatoren für die Alkenmetathese, the substituents R 27 , R 28 , R 29 , R 30 , R 3 , R 32 , R 33 , R 34 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, ci C 12 -alkoxycarbonyl, C 1 -C 12 -alkyl, aryl 5- to 18-membered, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl ) -amino, which in turn contain one or more identical or different C 1 -C 12 -alkyl , 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) -amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, Likewise provided by the present invention are complexes of general formula 10, methods for their preparation, and their use as precatalysts for alkene metathesis,
worin wherein
M, die Substituenten R , R2, R3, R4, R5, R6, R7, R8, R9, R 0 und R wie oben definiert sind und M, the substituents R, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 and R are as defined above and
die Substituenten R35, R36, R37, R38 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, C Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C Ci2-Alkyloxy, Di-(C C4-Alkyl)amino, Tri(C Ci2- Alkyl)silyl, Di(C -Ci2-Alkyl)(C6-C 8-Aryl)silyl, (Ci-Ci2-Alkyl)di(C6-Ci8-Aryl)silyl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d-Ci2-Alkyloxy, Di-(CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. the substituents R 35 , R 36 , R 37 , R 38 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, C 1 -C 2 -alkyl, 5- to 18-membered aryl, C 2 Ci alkyloxy, di- (CC 4 alkyl) amino, tri (C -C 2 - alkyl) silyl, di (C -C 2 alkyl) (C 6 -C 8 aryl) silyl, (Ci-Ci 2 alkyl) di (C 6 -C 8 aryl) silyl, in turn, with one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, d-Ci2 alkyloxy, di- ( C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
Beispiele für besonders bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formeln 11-16,
Examples of particularly preferred compounds in the context of the present invention are complexes of the general formulas 11-16,
R39 = Me, Phenyl. R 39 = Me, phenyl.
Ebenso sind Gegenstand der vorliegenden Erfindung Komplexe der allgemeinen Formel 17, Methoden zu deren Herstellung, sowie ihre Anwendung als Präkatalysatoren für die Alkenmetathese, Likewise provided by the present invention are complexes of the general formula 17, methods for their preparation, and their use as precatalysts for alkene metathesis,
M = Mo, W, M = Mo, W,
der Substituent R ausgewählt werden kann aus: Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können,
die Substituenten X, Y gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: Halogen, Methansulfonyloxy, Trifluormethansulfonyloxy, Benzolsulfonyloxy, Pyrrolyl, Ci-Ci2-Alkyloxy, 5- bis 18-glied riges Aryloxy, Tri(CrCi2- Alkyl)silyloxy, Di(CrCi2-Alkyl)(C6-Ci8-Aryl)silyloxy, (Ci-Ci2-Alkyl)di(C6-Ci8-Aryl)silyloxy, Tris(Ci-Ci2-Alkyloxy)silyloxy, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkoxy, Di-(Ci-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, der Substituent R2 ausgewählt werden kann aus den Resten: H, Ci-Ci2-Alkyl, 5- bis 18- gliedriges Aryl, wobei jeder dieser Reste seinerseits mit einem oder mehreren gleichen oder verschiedenen d-C^-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12 Alkyloxy, Di-(Ci-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein kann, der Substituent R3 ausgewählt werden kann aus den Resten: Ci-Ci2-Alkyl, 5- bis 18- gliedriges Aryl, wobei jeder dieser Reste seinerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(d-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein kann, die Substituenten R40, R4 , R42, R43, R44, R45, R46, R47 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12 Alkyloxy, Di-(CrC4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(Ci-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. the substituent R can be selected from Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn by one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, Ci-Ci 2- alkyloxy, di- (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, the substituents X, Y may be the same or different and can be independently selected from: halogen, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, pyrrolyl, Ci-Ci2 alkyloxy, 5- to 18-membered aryloxy, tri (CrCl 2 - alkyl ) silyloxy, di (CrCl 2 alkyl) (C 6 -C 8 aryl) silyloxy, (Ci-Ci2 alkyl) di (C 6 -C 8 aryl) silyloxy, tris (Ci-Ci2 alkyloxy) silyloxy, which in turn with one or more identical or different Ci-Ci 2 alkyl, 5- to 18-membered aryl, Ci-Ci 2 -alkoxy, di- (Ci-C 4 - alkyl) amino, halogen, trifluoromethyl, cyano , nitro radicals to be substituted, the substituent R 2 may be selected from the radicals: H, Ci-Ci 2 -alkyl, 5- to 18- membered aryl, wherein each of these radicals in turn by one or more identical or different dC ^ - alkyl, 5- to 18-membered aryl, C 1 -C 12 alkyloxy, di- (Ci-C 4 - alkyl) amino can, halogen, trifluoromethyl, cyano, nitro radicals to be substituted, the substituent R 3 a can be selected from the radicals: Ci-Ci 2 alkyl, 5- to 18-membered aryl, each of these radicals in turn with one or more identical or different Ci-Ci 2 alkyl, 5- to 18-membered aryl, Ci -C 12 -alkyloxy, di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, the substituents R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and may be independently selected from: H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci2 alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, C 1 C 12 alkyloxy, di- (C 1 -C 4 -alkyl) amino, which in turn with one or more identical or different Ci-Ci 2 alkyl, 5- to 18-membered aryl, Ci-Ci 2 -alkyloxy, di (Ci -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
Bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formel 18 Preferred compounds in the context of the present invention are complexes of the general formula 18
M = Mo, W, M = Mo, W,
die Substituenten R 2, R 3, R 4 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Trifluormethyl, Methyl, Ethyl, Propyl, Butyl, iso-Propyl, tert-Butyl, the substituents R 2 , R 3 , R 4 may be identical or different and may be selected independently of one another from: H, halogen, trifluoromethyl, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl,
die Substituenten R 5, R 6, R 7 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Ethyl, Propyl, Phenyl die Substituenten R 8, R 9, R20, R2 , R22, R23 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Trifluormethyl, die Substituenten R40, R4 , R42, R43, R44, R45, R46, R47 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Ci-C6-Alkyl, C1-C6the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R May be the same or different and may be independently selected from: H, methyl, trifluoromethyl, the substituents R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and independently of one another can be selected from: H, C 1 -C 6 -alkyl, C 1 -C 6
Alkyloxy, CrC6-Alkyloxycarbonyl, Phenyl, Halogen, Nitro. Alkyloxy, C 1 -C 6 alkyloxycarbonyl, phenyl, halogen, nitro.
Ebenfalls bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgem Also preferred compounds in the context of the present invention are complexes of the general
worin wherein
M = Mo, M = Mo,
die Substituenten R 5, R 6, R 7 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Ethyl, Propyl, Phenyl die Substituenten R 8, R 9, R20, R2 , R22, R23 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Methyl, Trifluormethyl, die Substituenten R40, R4 , R42, R43, R44, R45, R46, R47 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Ci-C6-Alkyl, C1-C6-the substituents R 5 , R 6 , R 7 may be identical or different and may be selected independently of one another from: H, methyl, ethyl, propyl, phenyl, the substituents R 8 , R 9 , R 20 , R 2 , R 22 , R May be the same or different and may be independently selected from: H, methyl, trifluoromethyl, the substituents R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and independently of one another can be selected from: H, Ci-C6-alkyl, C1-C6-
Alkyloxy, CrC6-Alkyloxycarbonyl, Phenyl, Halogen, Nitro. Alkyloxy, C 1 -C 6 alkyloxycarbonyl, phenyl, halogen, nitro.
Beispiele für bevorzugte 2,2'-Bipyridine (2,2'-Dipyridyle), die im Rahmen dieser Erfindung als Liganden zur Stabilisierung von Schrock-Alkyliden Komplexen des Molybdäns oder
Wolframs eingesetzt werden können, sind: 2,2'-Bipyridin, 5,5'-Dimethyl-2,2'-dipyridyl, 4,4'- Dimethyl-2,2'-dipyridyl, 6,6'-Dimethyl-2,2'-dipyridyl, 4-4'-Dimethoxy-2-2'-bipyridin, 2,2'- Bichinolin, 4,4'-Di-tert-butyl-2,2'-dipyridyl, 2,2'-Bipyridinyl-4,4'-dicarbonsäuredimethylester, 4,4'-Diphenyl-2,2'-dipyridyl, 6,6'-Dibromo-2,2'-dipyridyl, 4,4'-Dinonyl-2,2'-dipyridyl, 2,2'- Bichinolinyl-4,4'-dicarbonsäuredibutylester, 2,2'-Bichinolinyl-4,4'- dicarbonsäurediheptylester, 6-Methyl-2,2'-dipyridyl, 2-(2-Pyridinyl)chinolin, 2-Pyridin-2-yl- 4-pyrrolidin-1-yl-chinolin, 4-Piperidin-1-yl-2-pyridin-2-yl-chinolin, 4-Morpholin-4-yl-2- pyridin-2-yl-chinolin. Examples of preferred 2,2'-bipyridines (2,2'-dipyridyls), which in the context of this invention as ligands for the stabilization of Schrock alkylidene complexes of molybdenum or Tungsten can be used are: 2,2'-bipyridine, 5,5'-dimethyl-2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 6,6'-dimethyl-2 , 2'-dipyridyl, 4-4'-dimethoxy-2-2'-bipyridine, 2,2'-biquinoline, 4,4'-di-tert-butyl-2,2'-dipyridyl, 2,2'-di-tert-butyl-2,2'-bipyridyl Bipyridinyl-4,4'-dicarboxylic acid dimethyl ester, 4,4'-diphenyl-2,2'-dipyridyl, 6,6'-dibromo-2,2'-dipyridyl, 4,4'-dinonyl-2,2'-dipyridyl 2,2'-Biquinolinyl-4,4'-dicarboxylic acid dibutyl ester, 2,2'-biquinolinyl-4,4'-dicarboxylic acid di-heptyl ester, 6-methyl-2,2'-dipyridyl, 2- (2-pyridinyl) quinoline, 2 -Pyridin-2-yl-4-pyrrolidin-1-yl-quinoline, 4-piperidin-1-yl-2-pyridin-2-yl-quinoline, 4-morpholin-4-yl-2-pyridin-2-yl quinoline.
Besonders bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formel 20-23 Particularly preferred compounds in the context of the present invention are complexes of the general formula 20-23
R24 = Me, Ph R 24 = Me, Ph
R25, R26 = H , Me, CF3 R 25 , R 26 = H, Me, CF 3
Z = Methyl, iso-Propyl, Halogen. Z = methyl, iso-propyl, halogen.
Ebenso sind Gegenstand der vorliegenden Erfindung Komplexe der allgemeinen Formel 24, Methoden zu deren Herstellung, sowie ihre Anwendung als Präkatalysatoren für die Alkenmetathese, Likewise provided by the present invention are complexes of general formula 24, methods for their preparation, and their use as precatalysts for alkene metathesis,
worin
M, R1 , R2 und R3 sowie R27, R28, R29, R30, R3 , R32, R33, R34, R40, R4 , R42, R43, R44, R45, R46 und R47 wie oben definiert sind. wherein M, R 1 , R 2 and R 3 and R 27 , R 28 , R 29 , R 30 , R 3 , R 32 , R 33 , R 34 , R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are as defined above.
Ebenso sind Gegenstand der vorliegenden Erfindung Komplexe der allgemeinen Formel 25, Methoden zu deren Herstellung, sowie ihre Anwendung als Präkatalysatoren für die Alkenmetathese, Likewise provided by the present invention are complexes of general formula 25, methods for their preparation, and their use as precatalysts for alkene metathesis,
worin wherein
M, R1 , R2 und R3 sowie R35, R36, R37, R38, R40, R4 , R42, R43, R44, R45, R46 und R47 wie oben definiert sind. M, R 1 , R 2 and R 3 and R 35 , R 36 , R 37 , R 38 , R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are as defined above ,
Beispiele für besonders bevorzugte Verbindungen im Rahmen der vorliegenden Erfindung sind Komplexe der allgemeinen Formeln 26-31 Examples of particularly preferred compounds in the context of the present invention are complexes of the general formulas 26-31
R39 = Me, Phenyl. R 39 = Me, phenyl.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung der Verbindungen der allgemeinen Formeln I Another object of the present invention is a process for the preparation of the compounds of general formulas I.
M, X, Y, R1 , R2, R3, Ra, Rb, Rc, Rd, Re, Rf, R9, Rh wie oben definiert sind, M, X, Y, R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , R f , R 9 , R h are as defined above,
in welchem eine Verbindung der Formel 32 in which a compound of formula 32
worin wherein
M, X, Y, R-i , R2, R3 wie oben definiert sind, M, X, Y, Ri, R 2 , R 3 are as defined above,
mit einer Verbindung der allgemeinen Formel II with a compound of general formula II
Ra, Rb, Rc, Rd, Re, Rf, R9, Rh wie oben definiert sind, R a , R b , R c , R d , R e , R f , R 9 , R h are as defined above,
umgesetzt wird.
is implemented.
Schema 2. Beispiele zur Darstellung besonders bevorzugter Komplexe Scheme 2. Examples illustrating particularly preferred complexes
Beispiele für die Herstellung besonders bevorzugter Komplexe nach dem genannten Verfahren sind in Schema 2 gezeigt und werden im Abschnitt „Beispiele" im Detail beschrieben. Ebenfalls Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Nutzung der Komplexe der Formeln I, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 38, 40, 42, 43 als Präkatalysatoren zur Durchführung von Alkenmetathese Reaktionen durch Aktivierung mit einem geeigneten Additiv. Bei diesem Verfahren wird eine Lösung oder eine Suspension von Verbindung
der Formeln I, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 38, 40, 42, 43 in einem geeigneten Lösungsmittel mit wasserfreien Metallsalzen oder Metallkomplexen als Additiva umgesetzt, die ihrerseits stabile 1 , 10-Phenanthrolinkomplexe beziehungsweise 2,2'-Bipyridinkomplexe bilden. Diese Aktivierung erfolgt durch Dekomplexierung des jeweiligen 1 , 10-Phenanthrolin beziehungsweise 2,2'-Bipyridin Liganden vom Molybdän oder Wolfram unter Bildung der entsprechenden 1 ,10-Phenanthrolinkomplexe beziehungsweise 2,2'-Bipyridinkomplexe der verwendeten Additiva, welche wahlweise im Reaktionsgemisch verbleiben oder vor der Alkenmetathese aus dem Gemisch abgetrennt werden können. Für diese Aktivierung kommen alle wasserfreien Metallsalze oder Metallkomplexe in Betracht, die stabile 1 , 10- Phenanthrolinkomplexe beziehungsweise 2,2'-Bipyridinkomplexe bilden. Besonders bevorzugte Beispiele sind in Schema 3 sowie im Abschnitt„Beispiele" genannt. Examples of the preparation of particularly preferred complexes by the said process are shown in Scheme 2 and are described in detail in the "Examples" section Also a subject of the present invention is a process for the use of the complexes of the formulas I, 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 , 31, 38, 40, 42, 43 as precatalysts for carrying out alkene metathesis reactions by activation with a suitable additive In this process, a solution or a suspension of compound of the formulas I, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 38, 40, 42, 43 are reacted in a suitable solvent with anhydrous metal salts or metal complexes as additives, which in turn form stable 1, 10-phenanthroline complexes or 2,2'-Bipyridinkomplexe , This activation takes place by decomplexation of the respective 1, 10-phenanthroline or 2,2'-bipyridine ligands of molybdenum or tungsten to form the corresponding 1, 10-Phenanthrolinkomplexe or 2,2'-Bipyridinkomplexe of the additives used, which optionally remain in the reaction mixture or can be separated from the mixture before alkene metathesis. Suitable for this activation are all anhydrous metal salts or metal complexes which form stable 1, 10 phenanthroline complexes or 2,2'-bipyridine complexes. Particularly preferred examples are mentioned in Scheme 3 and in the section "Examples".
Zu den bevorzugten Additiva zählen: AIX3, MnX2, FeX2, FeX3, CoX2, CuX2, ZnX2, MgX2, NiX2, PdX2, PtX2, RuX2, RuX3, EuX3, mit X = F, Cl, Br, I, acetylacetonat, sulfat, sulfonat, nitrat, acetat, trifluoracetat, trifluormethansulfonat (triflat). Preferred additives include: AIX 3 , MnX 2 , FeX 2 , FeX 3 , CoX 2 , CuX 2 , ZnX 2 , MgX 2 , NiX 2 , PdX 2 , PtX 2 , RuX 2 , RuX 3 , EuX 3 , with X = F, Cl, Br, I, acetylacetonate, sulfate, sulfonate, nitrate, acetate, trifluoroacetate, trifluoromethanesulfonate (triflate).
Besonders bevorzugte Additiva sind: MgCI2, MgBr2, Mgl2, MnCI2, MnBr2, Mnl2, FeCI3, AICI3, CuCI2, ZnCI2, ZnBr2, Znl2, Zn(triflat)2, Zn(trifluoracetat)2. Particularly preferred additives are: MgCl 2 , MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , Mnl 2 , FeCl 3 , AICl 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znl 2 , Zn (triflate) 2 , Zn (trifluoroacetate 2 .
Abhängig vom gewählten Additiv und Addukt kann die Aktivierung bei unterschiedlichen Temperaturen durchgeführt werden, bevorzugt bei Temperaturen zwischen -20°C und + 140°C, besonders bevorzugt bei Temperaturen zwischen 20°C und 1 10°C. Als Lösungsmittel kommen alle Lösungsmittel in Betracht, die nicht zur Zersetzung der freigesetzten Schrock-Alkyliden Komplexen des Molybdäns oder Wolframs führen; bevorzugte Lösungsmittel sind Kohlenwasserstoffe, Halogenkohlenwasserstoffe und Ether; besonders bevorzugt sind Pentane, Hexane, Heptane, Octane, Petrolether, Benzol, Toluol, Xylole, Cumol, Decalin, Chlorbenzol, Brombenzol, Fluorbenzol, Trifluormethylbenzol, Dichlorbenzole, Trichlorbenzole, Dichlormethan, Chloroform, Tetrachlorkohlenstoff, 1 ,2-Dichlorethan, Tetrahydrofuran, 1 ,4-Dioxan, Dimethoxyethan, Diethylether, tert-Butylmethylether. Auch Mischungen dieser Lösungsmittel können eingesetzt werden.
Depending on the selected additive and adduct, the activation can be carried out at different temperatures, preferably at temperatures between -20 ° C and + 140 ° C, more preferably at temperatures between 20 ° C and 1 10 ° C. Suitable solvents are all solvents which do not lead to the decomposition of the liberated Schrock alkylidene complexes of molybdenum or tungsten; preferred solvents are hydrocarbons, halohydrocarbons and ethers; Particularly preferred are pentanes, hexanes, heptanes, octanes, petroleum ethers, benzene, toluene, xylenes, cumene, decalin, chlorobenzene, bromobenzene, fluorobenzene, trifluoromethylbenzene, dichlorobenzenes, trichlorobenzenes, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran, 1 , 4-dioxane, dimethoxyethane, diethyl ether, tert-butyl methyl ether. It is also possible to use mixtures of these solvents.
Schema 3. Beispiel der Aktivierung eines katalytisch inaktiven Addukts aus einem Schrock-Alkyliden und 1 , 10-Phenanthrolin (43) bzw. 2,2'-Bipyridin (38) unter Verwendung von ZnC als besonders bevorzugtem Additiv in Toluol als einem besonders bevorzugten Lösungsmittel gemäß der vorliegenden Erfindung. Erfolgt die Umsetzung in deuteriertem Toluol, so kann die Freisetzung des in der Alkenmetathese katalytisch aktiven Schrock- Alkylidens 37 durch H NMR Spektroskopie verfolgt werden. Beispiele Scheme 3. Example of activation of a catalytically inactive adduct from a Schrock alkylidene and 1, 10-phenanthroline (43) and 2,2'-bipyridine (38) using ZnC as a particularly preferred additive in toluene as a particularly preferred solvent according to the present invention. If the reaction is carried out in deuterated toluene, the release of the Schrock alkylidene 37 catalytically active in alkene metathesis can be monitored by H NMR spectroscopy. Examples
Abkürzung: phen = 1 ,10-Phenanthrolin; bipy = 2,2'-Bipyridin; dme = 1 ,2-Dimethoxyethan; biphen = biphenyl-2,2'-diolat; TMS = Trimethylsilyl; TBS = tert-Butyldimethylsilyl; TBDPS = tert-Butyldiphenylsilyl. Abbreviation: phen = 1, 10-phenanthroline; bipy = 2,2'-bipyridine; dme = 1, 2-dimethoxyethane; biphene = biphenyl-2,2'-diolate; TMS = trimethylsilyl; TBS = tert-butyldimethylsilyl; TBDPS = tert-butyldiphenylsilyl.
Die zur Darstellung der Komplexe verwendeten 2,2'-Bipyridin Derivate wurden in Toluol gelöst und die Lösung über Molsieb 5A (MS 5A) getrocknet. Anschließend wurde das Molsieb abfiltriert, das Filtrat eingeengt und das verbleibende 2,2'-Bipyridin Derivat unter Argon aufbewahrt. The 2,2'-bipyridine derivatives used to prepare the complexes were dissolved in toluene and the solution was dried over molecular sieve 5A (MS 5A). Subsequently, the molecular sieve was filtered off, the filtrate was concentrated and the remaining 2,2'-bipyridine derivative stored under argon.
Die zur Darstellung der Komplexe verwendeten 1 , 10-Phenanthrolin Derivate wurden entweder durch doppelte Sublimation im Hochvakuum gereinigt und getrocknet, oder in Toluol gelöst und die Lösung über Molsieb 5A (MS 5A) getrocknet; anschließend wurde das Toluol im Vakuum abdestilliert und das verbleibende 1 , 10-Phenanthrolin Derivat unter Argon aufbewahrt. The 1, 10-phenanthroline derivatives used to prepare the complexes were either purified by double sublimation under high vacuum and dried, or dissolved in toluene and the solution dried over molecular sieves 5A (MS 5A); then the toluene was distilled off in vacuo and the remaining 1, 10-phenanthroline derivative stored under argon.
Me(F3C)2Ca Me (F 3 C) 2 Ca
Me^CkCO'
[Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(phen)] (Ar = 2,6-diisopropylphenyl). Me ^ CKCO ' [Mo (CHC Me 2 Ph) (NAr) (OCMe (CF 3 ) 2 ) 2 (phen)] (Ar = 2,6-diisopropylphenyl).
Eine Lösung von [Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2] (326 mg, 426 μιηοΙ) in Toluol (3 mL) wurde zu einer Lösung von 1 , 10-Phenanthrolin (77 mg, 426 μιηοΙ) in Toluol (2 mL) zugegeben und das Gemisch 1 h bei Raumtemperatur gerührt. Anschließend wurde der gebildete Niederschlag abfiltriert und mit kaltem Toluol (ca. 2 mL) gewaschen. Die vereinten Filtrate wurden auf etwa ein Drittel des ursprünglichen Volumens eingeengt und anschließend auf -40°C abgekühlt, was eine zweite Charge an Komplex ergab. Die Chargen wurden vereinigt und im Vakuum getrocknet. Gelber Feststoff (384 mg, 95%). H NMR (400 MHz, CD2CI2): δ = 13.88 (s, 1 H), 9.48 (dd, J = 4.7, 1.6 Hz, 1 H), 8.41 (dd, J = 8.3, 1.6 Hz, 1 H), 8.37 (dd, J = 8.3, 1.6 Hz, 1 H), 7.98 (dd, J = 5.2, 1.3 Hz, 1 H), 7.92 (d, J = 8.9 Hz, 1 H), 7.86-7.82 (m, 2H), 7.67 (dd, J = 8.5, 1.0 Hz, 2H), 7.46 (t, J = 8.1 Hz, 2H), 7.33 (t, J = 7.3 Hz, 1 H), 7.30 (dd, J = 8.2, 5.6 Hz, 1 H), 6.91 (br s, 1 H), 6.80 (t, J = 7.6 Hz, 1 H), 6.71 (br s, 1 H), 4.38 (br s, 1 H), 3.13 (br s, 1 H), 2.07 (s, 3H), 1 .68 (s, 3H), 1.65 (s, 3H), 1.19 (br s, 6H), 0.85 (br s, 3H), 0.26 (s, 3H), -0.55 ppm (br s, 3H); 3C NMR (100 MHz, CD2CI2): δ = 309.6, 158.9, 150.5, 150.0, 149.6, 149.5, 145.8, 143.4, 139.3, 138.4, 138.0, 130.4, 129.9, 129.4, 128.7, 128.6, 127.9, 126.9, 126.7, 126.4, 126.3, 125.6, 125.1 , 124.9, 80.1 , 55.0, 32.0, 28.8, 28.2, 26.9, 26.6, 24.7, 24.3, 22.6, 21.5, 17.9, 17.6 ppm; 9F NMR (377 MHz, CD2CI2): δ = -76.3 (q, J = 10.3 Hz, 3F), -77.4 (m, 3F), -77.6 (q, J = 10.3 Hz, 3F), -77.9 ppm (m, 3F); IR (Film, cm ): 2966, 2868, 1578, 1424, 1296, 1214, 1 163, 1 105, 1070, 958, 844, 762, 727, 697. A solution of [Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3) 2 ) 2] (326 mg, 426 μιηοΙ) in toluene (3 mL) was added to a solution of 1, 10-phenanthroline (77 mg, 426 μιηοΙ) in toluene (2 mL) was added and the mixture was stirred for 1 h at room temperature. The precipitate formed was then filtered off and washed with cold toluene (about 2 ml). The combined filtrates were concentrated to about one-third of the original volume and then cooled to -40 ° C to give a second batch of complex. The batches were combined and dried in vacuo. Yellow solid (384 mg, 95%). H NMR (400 MHz, CD 2 CI 2 ): δ = 13.88 (s, 1H), 9.48 (dd, J = 4.7, 1.6 Hz, 1H), 8.41 (dd, J = 8.3, 1.6 Hz, 1H ), 8.37 (dd, J = 8.3, 1.6 Hz, 1 H), 7.98 (dd, J = 5.2, 1.3 Hz, 1 H), 7.92 (d, J = 8.9 Hz, 1 H), 7.86-7.82 (m , 2H), 7.67 (dd, J = 8.5, 1.0 Hz, 2H), 7.46 (t, J = 8.1 Hz, 2H), 7.33 (t, J = 7.3 Hz, 1 H), 7.30 (dd, J = 8.2 , 5.6 Hz, 1 H), 6.91 (br s, 1 H), 6.80 (t, J = 7.6 Hz, 1 H), 6.71 (br s, 1 H), 4.38 (br s, 1 H), 3.13 ( br s, 1 H), 2.07 (s, 3H), 1.68 (s, 3H), 1.65 (s, 3H), 1.19 (br s, 6H), 0.85 (br s, 3H), 0.26 (s, 3H), -0.55 ppm (br s, 3H); 3 C NMR (100 MHz, CD 2 Cl 2 ): δ = 309.6, 158.9, 150.5, 150.0, 149.6, 149.5, 145.8, 143.4, 139.3, 138.4, 138.0, 130.4, 129.9, 129.4, 128.7, 128.6, 127.9, 126.9 , 126.7, 126.4, 126.3, 125.6, 125.1, 124.9, 80.1, 55.0, 32.0, 28.8, 28.2, 26.9, 26.6, 24.7, 24.3, 22.6, 21.5, 17.9, 17.6 ppm; 9 F NMR (377 MHz, CD 2 CI 2 ): δ = -76.3 (q, J = 10.3 Hz, 3F), -77.4 (m, 3F), -77.6 (q, J = 10.3 Hz, 3F), 77.9 ppm (m, 3F); IR (Film, cm): 2966, 2868, 1578, 1424, 1296, 1214, 1 163, 1 105, 1070, 958, 844, 762, 727, 697.
Laut H NMR ist dieser Komplex nach vierwöchiger Lagerung bei Raumtemperatur an Luft zu ca. 50% intakt.
According to H NMR this complex is about 50% intact after four weeks storage at room temperature in air.
Abbildung 1. Struktur von [Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(phen)] Figure 1. Structure of [Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3 ) 2) 2 (phen)]
diisopropylphenyl) im Festkörper. diisopropylphenyl) in the solid state.
[Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(bipy)] (Ar = 2,6-diisopropylphenyl). [Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3 ) 2) 2 (bipy)] (Ar = 2,6-diisopropylphenyl).
Eine Lösung von [Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2] (360 mg, 470 pmol) in Toluol (3 mL) wurde zu einer Lösung von 2,2'-Bipyridin (73 mg, 470 pmol) in Toluol (2 mL) zugegeben und das Gemisch 1 h bei Raumtemperatur gerührt. Anschließend wurde der gebildete Niederschlag abfiltriert und mit kaltem Toluol (ca. 2 mL) gewaschen. Die vereinten Filtrate wurden auf etwa ein Drittel des ursprünglichen Volumens eingeengt und anschließend auf -40°C abgekühlt, was eine zweite Charge an Komplex ergab. Die Chargen wurden vereinigt und im Vakuum getrocknet. Gelber Feststoff (382 mg, 88%). 1H NMR (400 MHz, CD2CI2): δ = 13.74 (s, 1 H), 9.22 (dd, J = 5.1 , 1.6 Hz, 1 H), 8.02 (d, J = 8.0 Hz, 1 H), 7.97 (d, J = 8.1 Hz, 1 H), 7.92-7.84 (m, 2H), 7.76 (d, J = 4.6 Hz, 1 H), 7.62 (d, J = 8.2 Hz, 2H), 7.54 (ddd, J = 7.4, 5.2, 1.3 Hz, 1 H), 7.41 (t, J = 7.4 Hz, 2H), 7.28 (tt, J = 7.3, 1.2 Hz, 1 H), 6.96 (ddd, J = 7.4, 5.6, 1.3 Hz, 1 H), 9.92 (br s, 1 H), 6.88 (t, J = 7.0 Hz, 1 H), 6.84 (br s, 1 H), 4.19 (br s, 1 H), 3.16 (br s, 1 H), 2.02 (s, 3H), 1.63 (s, 3H), 1.61 (s, 3H),
1.24 (br s, 3H), 1.12 (br s, 3H), 0.81 (br s, 3H), 0.55 (s, 3H), -0.09 ppm (br s, 3H); 13C NMR (100 MHz, CD2CI2): δ = 309.0, 159.7, 154.9, 153.1 , 151.5, 150.3, 149.9, 149.7, 149.6, 148.0, 140.0, 139.2, 128.5, 126.8, 126.4, 126.3, 126.2, 122.8, 121.4, 80.1 , 54.8, 31.9, 28.7, 28.5, 26.9, 26.1 , 25.0, 24.5, 22.6, 17.7 ppm; 19F NMR (377 MHz, CD2CI2): δ = -76.4 (q, J = 10.3 Hz, 3F), -77.1 (q, J = 10.3 Hz, 3F), -77.4 (m, 3F), -77.7 ppm (m, 3F); IR (Film, ατϊ1): 2968, 2868, 1599, 1443, 1296, 1210, 1165, 1078, 1024, 955, 757, 697. A solution of [Mo (CHCMe2Ph) (NAr) (OCMe (CF 3) 2) 2] (360 mg, 470 pmol) in toluene (3 mL) was added to a solution of 2,2'-bipyridine (73 mg, 470 pmol) in toluene (2 mL) and the mixture stirred at room temperature for 1 h. The precipitate formed was then filtered off and washed with cold toluene (about 2 ml). The combined filtrates were concentrated to about one-third of the original volume and then cooled to -40 ° C to give a second batch of complex. The batches were combined and dried in vacuo. Yellow solid (382 mg, 88%). 1 H NMR (400 MHz, CD 2 CI 2 ): δ = 13.74 (s, 1 H), 9.22 (dd, J = 5.1, 1.6 Hz, 1 H), 8.02 (d, J = 8.0 Hz, 1 H) , 7.97 (d, J = 8.1 Hz, 1H), 7.92-7.84 (m, 2H), 7.76 (d, J = 4.6 Hz, 1H), 7.62 (d, J = 8.2 Hz, 2H), 7.54 ( ddd, J = 7.4, 5.2, 1.3 Hz, 1 H), 7.41 (t, J = 7.4 Hz, 2H), 7.28 (tt, J = 7.3, 1.2 Hz, 1 H), 6.96 (ddd, J = 7.4, 5.6, 1.3 Hz, 1 H), 9.92 (br s, 1 H), 6.88 (t, J = 7.0 Hz, 1 H), 6.84 (br s, 1 H), 4.19 (br s, 1 H), 3.16 (brs, 1H), 2.02 (s, 3H), 1.63 (s, 3H), 1.61 (s, 3H), 1.24 (br s, 3H), 1.12 (br s, 3H), 0.81 (br s, 3H), 0.55 (s, 3H), -0.09 ppm (br s, 3H); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 309.0, 159.7, 154.9, 153.1, 151.5, 150.3, 149.9, 149.7, 149.6, 148.0, 140.0, 139.2, 128.5, 126.8, 126.4, 126.3, 126.2, 122.8 , 121.4, 80.1, 54.8, 31.9, 28.7, 28.5, 26.9, 26.1, 25.0, 24.5, 22.6, 17.7 ppm; 19 F NMR (377 MHz, CD 2 CI 2 ): δ = -76.4 (q, J = 10.3 Hz, 3F), -77.1 (q, J = 10.3 Hz, 3F), -77.4 (m, 3F), 77.7 ppm (m, 3F); IR (film, ατϊ 1 ): 2968, 2868, 1599, 1443, 1296, 1210, 1165, 1078, 1024, 955, 757, 697.
Laut 1H NMR ist dieser Komplex nach vierwöchiger Lagerung bei Raumtemperatur an Luft intakt und zeigt keine (< 5%) erkennbare Zersetzung. According to 1 H NMR, this complex is intact after 4 weeks' storage at room temperature in air and shows no (<5%) detectable decomposition.
Abbildung 2. Struktur von [Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(bipy)] Figure 2. Structure of [Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3 ) 2 ) 2 (bipy)]
diisopropylphenyl) im Festkörper. diisopropylphenyl) in the solid state.
[Mo CH-rBu)(NAr)(OSiPh3)2(phen)] (Ar = 2,6-diisopropylphenyl). [Mo CH-rBu) (NAr) (OSiPh 3 ) 2 (phen)] (Ar = 2,6-diisopropylphenyl).
Eine Lösung von Ph3SiOK (302 mg, 959 pmol) in Toluol (5 mL) wurde zu einer Lösung von [Mo(CH-fBu)(NAr)(OS02CF3)2(dme)] (350 mg, 480 μηηοΙ) in Toluol (5 mL) zugegeben
und das Gemisch 1 h bei Raumtemperatur gerührt. Anschließend wurde der gebildete Niederschlag abfiltriert und das Filtrat zu einer Lösung von 1 ,10 - Phenanthrolin (87 mg, 480 Mmol) in Toluol (5 mL) gegeben. Das Gemisch wurde 1 h gerührt, anschließend das Lösungsmittel abgezogen, der Rückstand in wenig CH2CI2 (~ 5 mL) gelöst und das Produkt durch Zugabe von Pentan (25 mL) gefällt. Der Niederschlag wurde abfiltriert und im Vakuum getrocknet. Gelber Feststoff (417 mg, 81%). 1H NMR (400 MHz, CD2CI2): δ = 13.63 (s, 1 H), 9.76 (dd, J = 4.7, 1.6 Hz, 1 H), 9.30 (dd, J = 5.1 , 1.5 Hz, 1 H), 8.26 (dd, J = 8.2, 1.6 Hz, 1 H), 7.94 (dd, J = 8.2, 1.4 Hz, 1 H), 7.84 (dd, J = 8.0, 1.4 Hz, 6H), 7.72 (d J = 8.8 Hz, 1 H), 7.61 (dd, J = 8.2, 4.7 Hz, 1 H), 7.50 (d, J = 8.8 Hz, 1 H), 7.41 (dd, J = 8.2, 5.2 Hz, 1 H), 7.23 (tt, J = 7.4, 1.4 Hz, 3H), 7.08-7.03 (m, 9H), 7.00 (dd, J = 8.0, 1.4 Hz, 6H), 6.80 (t, J = 7.4 Hz, 6H), 6.72-6.71 (m, 3H), 4.37 (br s, 1 H), 3.66 (br s, 1 H), 1.20 (s, 9H), 1.14 (br s, 3H), 0.50 (br s, 6H), -043 ppm (br s, 3H);13C NMR (100 MHz, CD2CI2): δ = 304.9, 158.1 , 150.2, 149.5, 145.0, 143.3, 141.4, 140.6, 138.6, 137.4, 136.7, 135.5, 135.3, 130.5, 130.1 , 130.0, 128.5, 128.3, 128.0, 127.5, 127.4, 127.2, 127.0, 125.2, 124.9, 124.2, 123.1 , 49.0, 32.0 ppm; IR (Film, cm"1): 2936, 2866, 1513, 1423, 1256, 1144, 1106, 1032, 947, 842, 760, 698. A solution of Ph 3 SiOK (302 mg, 959 pmol) in toluene (5 mL) was added to a solution of [Mo (CH-fBu) (NAr) (OSO 2 CF 3 ) 2 (dme)] (350 mg, 480 μηηοΙ) in toluene (5 mL) was added and the mixture stirred for 1 h at room temperature. The formed precipitate was then filtered off and the filtrate added to a solution of 1, 10-phenanthroline (87 mg, 480 mmol) in toluene (5 mL). The mixture was stirred for 1 h, then the solvent was stripped off, the residue was dissolved in a little CH 2 Cl 2 (~ 5 mL) and the product was precipitated by the addition of pentane (25 mL). The precipitate was filtered off and dried in vacuo. Yellow solid (417 mg, 81%). 1 H NMR (400 MHz, CD 2 CI 2 ): δ = 13.63 (s, 1 H), 9.76 (dd, J = 4.7, 1.6 Hz, 1 H), 9.30 (dd, J = 5.1, 1.5 Hz, 1 H), 8.26 (dd, J = 8.2, 1.6Hz, 1H), 7.94 (dd, J = 8.2, 1.4Hz, 1H), 7.84 (dd, J = 8.0, 1.4Hz, 6H), 7.72 (i.e. J = 8.8 Hz, 1 H), 7.61 (dd, J = 8.2, 4.7 Hz, 1 H), 7.50 (d, J = 8.8 Hz, 1 H), 7.41 (dd, J = 8.2, 5.2 Hz, 1 H ), 7.23 (tt, J = 7.4, 1.4Hz, 3H), 7.08-7.03 (m, 9H), 7.00 (dd, J = 8.0, 1.4Hz, 6H), 6.80 (t, J = 7.4Hz, 6H) , 6.72-6.71 (m, 3H), 4.37 (br s, 1 H), 3.66 (br s, 1 H), 1.20 (s, 9H), 1.14 (br s, 3H), 0.50 (br s, 6H) , -043 ppm (br s, 3H); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 304.9, 158.1, 150.2, 149.5, 145.0, 143.3, 141.4, 140.6, 138.6, 137.4, 136.7, 135.5, 135.3, 130.5, 130.1, 130.0, 128.5, 128.3 , 128.0, 127.5, 127.4, 127.2, 127.0, 125.2, 124.9, 124.2, 123.1, 49.0, 32.0 ppm; IR (film, cm -1 ): 2936, 2866, 1513, 1423, 1256, 1144, 1106, 1032, 947, 842, 760, 698.
[ )(OSiPh3)2(phen)] (Ar = 2,6-diisopropylphenyl). [(OSiPh 3 ) 2 (phen)] (Ar = 2,6-diisopropylphenyl).
Hergestellt wie oben beschrieben aus Ph3SiOK (300 mg, 955 pmol), [Mo(CHCMe2Ph)(NAr)(OS02CF3)2(dme)] (378 mg, 477 pmol) und 1 ,10 - Phenanthrolin (86 mg, 477 pmol). Gelber Feststoff (460 mg, 85%). 1H NMR (400 MHz, CD2CI2): δ = 13.61 (s, 1 H), 9.78 (dd, J = 4.7, 1.6 Hz, 1 H), 8.22 (dd, J = 8.2, 1.5 Hz, 1 H), 7.91 (dd, J = 5.2, 1.5 Hz, 1 H), 7.85 (dd, J = 8.0, 1.4 Hz, 6H), 7.76 (dd, J = 8.2, 1.5 Hz, 1 H), 7.62-7.58 (m, 4H), 7.48 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 8.8 Hz, 1 H), 7.25 (tt, J = 7.4, 1.4 Hz, 3H), 7.09-7.02 (m, 10H), 6.91 (dd, J = 8.0, 1.4 Hz, 6H), 6.86 (dd, J = 5.1 , 3.0 Hz, 1 H), 6.77 (t, J = 7.6 Hz, 6H), 6.74 (m, 3H), 4.53 (br s, 1 H), 3.20 (br s, 1 H), 2.20 (s, 3H), 1.20 (br s, 3H), 0.93 (s, 3H), 0.56 (br s, 6H), -0.67 ppm (br s, 3H); 13C NMR (100 MHz, CD2CI2): δ = 300.2, 157.5, 151.4, 150.2, 149.3, 144.6, 143.2, 141.4, 140.4, 138.3, 137.4, 136.7, 136.3, 135.4, 135.3, 130.5, 129.9, 129.8, 128.6, 128.3, 128.0, 127.8, 127.5, 127.4, 127.2, 127.0,
Prepared as described above from Ph 3 SiO 2 (300 mg, 955 pmol), [Mo (CHC Me 2 Ph) (NAr) (OSO 2 CF 3 ) 2 (dme)] (378 mg, 477 pmol) and 1, 10-phenanthroline (86 mg, 477 pmol). Yellow solid (460 mg, 85%). 1 H NMR (400 MHz, CD 2 CI 2 ): δ = 13.61 (s, 1 H), 9.78 (dd, J = 4.7, 1.6 Hz, 1 H), 8.22 (dd, J = 8.2, 1.5 Hz, 1 H), 7.91 (dd, J = 5.2, 1.5 Hz, 1 H), 7.85 (dd, J = 8.0, 1.4 Hz, 6H), 7.76 (dd, J = 8.2, 1.5 Hz, 1 H), 7.62-7.58 (m, 4H), 7.48 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 8.8 Hz, 1H), 7.25 (tt, J = 7.4, 1.4 Hz, 3H), 7.09-7.02 (m , 10H), 6.91 (dd, J = 8.0, 1.4 Hz, 6H), 6.86 (dd, J = 5.1, 3.0 Hz, 1 H), 6.77 (t, J = 7.6 Hz, 6H), 6.74 (m, 3H ), 4.53 (br s, 1 H), 3.20 (br s, 1 H), 2.20 (s, 3H), 1.20 (br s, 3H), 0.93 (s, 3H), 0.56 (br s, 6H), -0.67 ppm (br s, 3H); 13 C NMR (100 MHz, CD 2 Cl 2 ): δ = 300.2, 157.5, 151.4, 150.2, 149.3, 144.6, 143.2, 141.4, 140.4, 138.3, 137.4, 136.7, 136.3, 135.4, 135.3, 130.5, 129.9, 129.8 , 128.6, 128.3, 128.0, 127.8, 127.5, 127.4, 127.2, 127.0,
Abbildung 3. Struktur von [Mo(CHCMe2Ph)(NAr)(OSiPh3)2(phen)] (Ar = 2,6- diisopropylphenyl) im Festkörper. Der Kristall enthält ko-kristallisiertes CH2CI2. -(+)-fBu2Me4(biphen))(bipy)] (Ar = 2,6-diisopropylphenyl). Figure 3. Structure of [Mo (CHCMe 2 Ph) (NAr) (OSiPh 3 ) 2 (phen)] (Ar = 2,6-diisopropylphenyl) in the solid state. The crystal contains co-crystallized CH 2 Cl 2 . - (+) - fBu 2 Me 4 (biphene)) (bipy)] (Ar = 2,6-diisopropylphenyl).
Eine Lösung von [Mo(CHCMe2Ph)(NAr)((f?)-(+)-terf-Bu2Me4(biphen)] (316 mg, 418 mol) in Et20 (3 mL) wurde zu einer Lösung von 2,2'-Bipyridin (65 mg, 418 mol) in Et20 (2 mL) zugegeben und das Gemisch 1 h bei Raumtemperatur gerührt. Anschließend wurde das Lösungsmittel abgezogen und der Rückstand durch Umkristallisation aus Pentan bei - 40°C gereinigt. Nach Trocknen im Vakuum erhält man den gewünschten Komplex als orange-roten Feststoff (282 mg, 74%). 1H NMR (400 MHz, CD2CI2): δ = 13.03 (s, 1 H), 8.62 (dd, J = 5.2, 1 .8 Hz, 1 H), 7.87 (d, J = 8.0 Hz, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 7.74-7.68
(m, 2H), 7.56 (dd, J = 8.5, 1.2 Hz, 2H), 7.36-7.31 (m, 3H), 7.19 (tt, J = 7.2, 1.2 Hz, 1 H), 6.98 (s, 1 H), 6.94 (ddd, J = 7.4, 5.2, 1.1 Hz, 1 H), 6.83 (ddd, J = 7.4, 5.4, 1.2 Hz, 1 H), 6.79- 6.74 (m, 3H), 6.35 (s, 1 H), 4.18 (br s, 1 H), 3.65 (br s, 1 H), 2.24 (s, 3H), 2.12 (s, 3H), 1.73 (s, 3H), 1.57 (s, 3H), 1.54 (s, 3H), 1.49 (s, 9H), 1.28 (br s, 3H), 1.04 (s, 6H), 0.71 (br s, 3H), 0.68 (s, 9H), -0.01 ppm (br s, 3H); 3C NMR (100 MHz, CD2CI2): δ = 305.3, 168.6, 162.2, 157.9, 154.4, 151.9, 151.6, 150.7, 150.4, 149.5, 148.8, 148.6, 146.9, 138.7, 138.4,A solution of [Mo (CHC Me 2 Ph) (NAr) ((f) - (+) - terf -Bu 2 Me 4 (biphene)] (316 mg, 418 mol) in Et 2 O (3 mL) became of a solution of 2,2'-bipyridine (65 mg, 418 mol) in Et 2 O (2 mL) and the mixture was stirred at room temperature for 1 h, then the solvent was removed and the residue was recrystallized from pentane at -40 ° After drying in vacuo, the desired complex is obtained as an orange-red solid (282 mg, 74%). 1 H NMR (400 MHz, CD 2 CI 2 ): δ = 13.03 (s, 1H), 8.62 ( dd, J = 5.2, 1 .8 Hz, 1 H), 7.87 (d, J = 8.0 Hz, 1 H), 7.79 (d, J = 8.2 Hz, 1 H), 7.74-7.68 (m, 2H), 7.56 (dd, J = 8.5, 1.2Hz, 2H), 7.36-7.31 (m, 3H), 7.19 (tt, J = 7.2, 1.2Hz, 1H), 6.98 (s, 1H ), 6.94 (ddd, J = 7.4, 5.2, 1.1 Hz, 1 H), 6.83 (ddd, J = 7.4, 5.4, 1.2 Hz, 1 H), 6.79- 6.74 (m, 3H), 6.35 (s, 1 H), 4.18 (br s, 1 H), 3.65 (br s, 1 H), 2.24 (s, 3H), 2.12 (s, 3H), 1.73 (s, 3H), 1.57 (s, 3H), 1.54 (s, 3H), 1.49 (s, 9H), 1.28 (br s, 3H), 1.04 (s, 6H), 0.71 (br s, 3H), 0.68 (s, 9H), -0.01 ppm (br s, 3H); 3 C NMR (100 MHz, CD 2 CI 2 ): δ = 305.3, 168.6, 162.2, 157.9, 154.4, 151.9, 151.6, 150.7, 150.4, 149.5, 148.8, 148.6, 146.9, 138.7, 138.4,
137.2, 133.8, 133.6, 133.2, 132.4, 132.0, 131.5, 129.2, 128.4, 127.2, 126.4, 125.7, 125.4,137.2, 133.8, 133.6, 133.2, 132.4, 132.0, 131.5, 129.2, 128.4, 127.2, 126.4, 125.7, 125.4,
125.3, 125.0, 124.9, 124.8, 122.6, 122.0, 121.2, 35.0, 34.8, 34.5, 32.1 , 32.0, 31.5, 29.7, 27.4, 26.4, 25.2, 24.2, 22.6, 20.3, 20.1 , 19.9, 16.4, 16.0, 15.8, 14.2 ppm; IR (Film, cm"1): 2920, 2862, 1738, 1595, 1408, 1261 , 1040, 974, 859, 798, 756, 702. 125.3, 125.0, 124.9, 124.8, 122.6, 122.0, 121.2, 35.0, 34.8, 34.5, 32.1, 32.0, 31.5, 29.7, 27.4, 26.4, 25.2, 24.2, 22.6, 20.3, 20.1, 19.9, 16.4, 16.0, 15.8, 14.2 ppm; IR (film, cm "1 ): 2920, 2862, 1738, 1595, 1408, 1261, 1040, 974, 859, 798, 756, 702.
Abbildung 4. Struktur von [Mo(CHCMe2Ph)(NAr)((R)-(+)-fBu2Me4(biphen))(bipy)] (Ar = 2,6- diisopropylphenyl) im Festkörper. Ringschluss-Olefin Metathese mit Hilfe vonFigure 4. Structure of [Mo (CHCMe 2 Ph) (NAr) ((R) - (+) - fBu 2 Me 4 (biphene) (bipy)] (Ar = 2,6-diisopropylphenyl) in the solid state. Ring-closing olefin metathesis using
[Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(phen)] in Gegenwart von ZnCI2 (Ar = 2,6- diisopropylphenyl)). Eine Lösung von [Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(phen)] (24 mg, 25 pmol, 5 mol%) and wasserfreiem ZnCI2 (3.4 mg, 25 μηηοΙ) in Toluol (2.5 mL) wurde unter Argon für 30 min auf 100°C erhitzt. Nach dieser Aktivierungsphase wurde das Gemisch auf Raumtempertur abgekühlt bevor Diethyl 2,2-diallylmalonat (121 pL, 500 pmol) zugegeben wurde. Danach wurde weitere 30 min bei Raumtemperatur gerührt, anschließend das Lösungsmittel abgezogen und der Rückstand säulenchromatographisch
gereinigt. Man erhielt Diethylcyclopent-3-en-1 ,1-dicarboxylat als farbloses Öl (104 mg, 98%).1H NMR (400 MHz, CDCI3): δ = 5.59 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 3.00 (s, 4H), 1.24 ppm (t, J = 7.1 Hz, 6H); 13C NMR (100 MHz, CDCI3): δ = 172.4, 127.9, 61.6, 59.0, 41.0, 14.2 ppm; IR (Film, cm"1): 3463, 2982, 2872, 1728, 1446, 1366, 1248, 1179, 1060, 1015, 951 , 695; MS (El) m/z (%): 212 [M+] (25), 166 (45), 138 (100), 1 11 (41), 93 (39), 79 (56), 66 (76), 55 (5), 39 (16), 29 (97); HRMS (ESI): m/z: berechnet für CnH1604 + Na: 235.0946; gefunden: 235.0941. Die erhaltenen Daten entsprechen jenen der Literatur (T. Kirkland, R. H. Grubbs, J. Org. Chem. 1997, 62, 7310-7318). Diethyl-3,4-dimethylcyclopent-3-en-1,1-dicarboxylat.
[Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3 ) 2 ) 2 (phen)] in the presence of ZnCl 2 (Ar = 2,6-diisopropylphenyl)). A solution of [Mo (CHC Me 2 Ph) (NAr) (OCMe (CF 3 ) 2 ) 2 (phen)] (24 mg, 25 pmol, 5 mol%) and anhydrous ZnCl 2 (3.4 mg, 25 μηηοΙ) in toluene (2.5 mL) was heated to 100 ° C under argon for 30 min. After this activation phase, the mixture was cooled to room temperature before diethyl 2,2-diallylmalonate (121 pL, 500 pmol) was added. Thereafter, the mixture was stirred at room temperature for a further 30 min, then the solvent was stripped off and the residue was purified by column chromatography cleaned. Diethyl cyclopent-3-ene-1,1-dicarboxylate was obtained as a colorless oil (104 mg, 98%). 1 H NMR (400 MHz, CDCl 3 ): δ = 5.59 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 3.00 (s, 4H), 1.24 ppm (t, J = 7.1 Hz, 6H ); 13 C NMR (100 MHz, CDCl 3 ): δ = 172.4, 127.9, 61.6, 59.0, 41.0, 14.2 ppm; IR (film, cm -1 ): 3463, 2982, 2872, 1728, 1446, 1366, 1248, 1179, 1060, 1015, 951, 695; MS (El) m / z (%): 212 [M + ] ( 25), 166 (45), 138 (100), 11 (41), 93 (39), 79 (56), 66 (76), 55 (5), 39 (16), 29 (97); HRMS (ESI): m / z: calculated for CnH 16 O 4 + Na: 235.0946; found: 235.0941 The data obtained correspond to those of the literature (T. Kirkland, RH Grubbs, J. Org. Chem. 1997, 62, 7310- 7318). Diethyl 3,4-dimethylcyclopent-3-ene-1,1-dicarboxylate.
Analog hergestellt als farbloses ÖI.1H NMR (400 MHz, CDCI3): δ = 4.18 (q, J = 7.1 Hz, 4H), 2.92 (s, 4H), 1.58 (s, 6H), 1.23 ppm (t, J = 7.1 Hz, 6H); 13C NMR (100 MHz, CDCI3): δ = 172.7, 128.2, 122.9, 61.5, 57.3, 46.0, 28.1 , 22.6, 14.2, 13.4 ppm; IR (Film, cm"1): 3462, 2970, 2859, 1729, 1443, 1366, 1246, 1180, 1071 , 1019; MS (El) m/z (%): 240 [M+] (26), 195 (7), 166 (100), 138 (11 ), 121 (23), 107 (15), 93 (42), 79 (17), 29 (30); HRMS (ESI): m/z: berechnet für C 3H20O4 + Na: 263.1259; gefunden: 263.1254. Die erhaltenen Daten entsprechen jenen der Literatur (T. Kirkland, R. H. Grubbs, J. Org. Chem. 1997, 62, 7310- 7318). Analogously prepared as a colorless oil. 1 H NMR (400 MHz, CDCl 3 ): δ = 4.18 (q, J = 7.1 Hz, 4H), 2.92 (s, 4H), 1.58 (s, 6H), 1.23 ppm (t, J = 7.1 Hz, 6H ); 13 C NMR (100 MHz, CDCl 3 ): δ = 172.7, 128.2, 122.9, 61.5, 57.3, 46.0, 28.1, 22.6, 14.2, 13.4 ppm; IR (film, cm -1 ): 3462, 2970, 2859, 1729, 1443, 1366, 1246, 1180, 1071, 1019; MS (El) m / z (%): 240 [M + ] (26), 195 (7), 166 (100), 138 (11), 121 (23), 107 (15), 93 (42), 79 (17), 29 (30); HRMS (ESI): m / z: calculated for C 3 H 20 O 4 + Na: 263.1259; found: 263.1254 The data obtained correspond to those of the literature (T. Kirkland, RH Grubbs, J. Org. Chem. 1997, 62, 7310-7318).
Diethyl-3-fert-butylcyclopent-3-en-1 ,1-dicarboxylat.
Diethyl 3-tert-butylcyclopent-3-ene-1, 1-dicarboxylate.
Analog hergestellt als farbloses Öl. 1H NMR (400 MHz, CDCI3): δ = 5.17 (s, 1 H), 4.18 (q, J = 7.1 Hz, 4H), 2.94 (s, 4H), 1.23 (t, J = 7.1 Hz, 6H), 1.04 ppm (s, 9H);13C NMR (100 MHz, CDCI3): δ = 172.4, 151.1 , 117.6, 61.5, 59.6, 40.3, 39.9, 32.8, 29.0, 14.2 ppm; IR (Film, cm" 1): 3462, 2964, 2869, 1730, 1446, 1364, 1245, 1183, 1060, 1024, 815, 737; MS (El) m/z (%): 268 [M+] (24), 223 (8), 194 (58), 179 (82), 151 (14), 138 (20), 133 (22), 121 (100), 107 (82), 91 (21), 79 (12), 65 (7), 57 (26), 41 (14), 29 (58); HRMS (ESI): m/z: berechnet für C15H24O4 + Na: 291.1572; gefunden: 291.1567. Die erhaltenen Daten entsprechen jenen der Literatur (T. Kirkland, R. H. Grubbs, J. Org. Chem. 1997, 62, 7310-7318).
hylcyclohept-3-en-1 ,1 -dicarboxylat.
Analogously prepared as a colorless oil. 1 H NMR (400 MHz, CDCl 3 ): δ = 5.17 (s, 1 H), 4.18 (q, J = 7.1 Hz, 4H), 2.94 (s, 4H), 1.23 (t, J = 7.1 Hz, 6H ), 1.04 ppm (s, 9H); 13 C NMR (100 MHz, CDCl 3 ): δ = 172.4, 151.1, 117.6, 61.5, 59.6, 40.3, 39.9, 32.8, 29.0, 14.2 ppm; IR (Film, cm "1): 3462, 2964, 2869, 1730, 1446, 1364, 1245, 1183, 1060, 1024, 815, 737; MS (El) m / z (%): (268 [M +] 24), 223 (8), 194 (58), 179 (82), 151 (14), 138 (20), 133 (22), 121 (100), 107 (82), 91 (21), 79 ( 12), 65 (7), 57 (26), 41 (14), 29 (58); HRMS (ESI): m / z: Calcd for C15H24O4 + Na: 291.1572; Found: 291.1567 Literature (T. Kirkland, RH Grubbs, J. Org. Chem. 1997, 62, 7310-7318). hylcyclohept-3-en-1, 1-dicarboxylate.
Analog hergestellt als farbloses Öl. 1H NMR (400 MHz, CDCI3): δ = 5.57 (t, J = 6.2 Hz, 1 H), 4.16 (q, J = 7.1 Hz, 4H), 2.64 (s, 2H), 2.19-2.16 (m, 2H), 2.07-2.03 (m, 2H), 1.75 (s, 3H), 1.65-1.59 (m, 2H), 1.23 ppm (t, J = 7.1 Hz, 6H); 13C NMR (100 MHz, CDCI3): δ = 172.0, 135.2, 127.7, 61.2, 55.8, 37.6, 36.9, 28.0, 26.7, 22.9, 14.2 ppm; IR (Film, cm'1): 3463, 2970, 2862, 1729, 1446, 1366, 1310, 1217, 1090, 1056, 1030; MS (El) m/z (%): 254 [M+] (15), 208 (20), 180 (22), 173 (100), 163 (14), 152 (7), 135 (15), 127 (28), 107 (33), 91 (9), 79 (11); HRMS (ESI): m/z: berechnet für C14H2204 + Na: 277.1416; gefunden: 277.1410. Die erhaltenen Daten entsprechen jenen der Literatur (T. Kirkland, R. H. Grubbs, J. Org. Chem. 1997, 62, 7310-7318). Analogously prepared as a colorless oil. 1 H NMR (400 MHz, CDCl 3 ): δ = 5.57 (t, J = 6.2 Hz, 1H), 4.16 (q, J = 7.1 Hz, 4H), 2.64 (s, 2H), 2.19-2.16 (m , 2H), 2.07-2.03 (m, 2H), 1.75 (s, 3H), 1.65-1.59 (m, 2H), 1.23 ppm (t, J = 7.1 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ): δ = 172.0, 135.2, 127.7, 61.2, 55.8, 37.6, 36.9, 28.0, 26.7, 22.9, 14.2 ppm; IR (film, cm '1 ): 3463, 2970, 2862, 1729, 1446, 1366, 1310, 1217, 1090, 1056, 1030; MS (El) m / z (%): 254 [M + ] (15), 208 (20), 180 (22), 173 (100), 163 (14), 152 (7), 135 (15), 127 (28), 107 (33), 91 (9), 79 (11); HRMS (ESI): m / z: calculated for C 14 H 2 O 4 + Na: 277.1416; found: 277.1410. The data obtained correspond to those of the literature (T. Kirkland, RH Grubbs, J. Org. Chem. 1997, 62, 7310-7318).
2,2-Dimethyl-6-phenyl-1-oxa-2-silacyclohex-3-en.
Analog hergestellt als farbloses Öl; die Reinigung erfolgte durch Kugelrohrdestillation (bp = 93-95°C, 0.4 Torr). 1H NMR (400 MHz, CDCI3): δ = 7.43(dd, J = 8.8, 1.6 Hz, 2H), 7.37 (td, J = 8.8, 1.6 Hz, 2H), 7.27 (tt, J = 8.8, 1.6 Hz, 1 H), 6,86 (ddd, J = 14.0, 6.0, 2.4 Hz, 1 H), 5.89 (ddd, J = 14.0, 2.8, 0.8 Hz, 1 H), 5.02 (dd, J = 10.0, 3.6 Hz, 1 H), 2.47-2.33 (m, 2H), 0.28 (s, 3H), 0.27 ppm (s, 3H); 13C NMR (100 MHz, CDCI3): δ = 147.2, 144.6, 128.5, 127.6, 127.3, 125.7, 73.5, 39.1 , 0.0, -0.4 ppm; IR (Film, cm"1): 2958, 2855, 1587, 1249, 1062, 955, 833, 785, 695; MS (El) m/z (%): 204 [M+] (43), 189 (5), 130 (100), 111 (5), 98 (40), 83 (25), 75 (6), 61 (5); HRMS (ESI): m/z: berechnet für C12H16OSi: 204.0970; gefunden: 204.0970. Die erhaltenen Daten entsprechen jenen der Literatur (S. E. Denmark, S.-M. Yang, Org. Lett. 2001 , 3, 1749-1752). 2,2-dimethyl-6-phenyl-1-oxa-2-silacyclohex-3-ene. Analogously prepared as a colorless oil; the purification was carried out by Kugelrohr distillation (bp = 93-95 ° C, 0.4 Torr). 1 H NMR (400 MHz, CDCl 3 ): δ = 7.43 (dd, J = 8.8, 1.6 Hz, 2H), 7.37 (td, J = 8.8, 1.6 Hz, 2H), 7.27 (tt, J = 8.8, 1.6 Hz, 1 H), 6.86 (ddd, J = 14.0, 6.0, 2.4 Hz, 1 H), 5.89 (ddd, J = 14.0, 2.8, 0.8 Hz, 1 H), 5.02 (dd, J = 10.0, 3.6Hz, 1H), 2.47-2.33 (m, 2H), 0.28 (s, 3H), 0.27ppm (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 147.2, 144.6, 128.5, 127.6, 127.3, 125.7, 73.5, 39.1, 0.0, -0.4 ppm; IR (film, cm -1 ): 2958, 2855, 1587, 1249, 1062, 955, 833, 785, 695; MS (El) m / z (%): 204 [M + ] (43), 189 (5 ), 130 (100), 111 (5), 98 (40), 83 (25), 75 (6), 61 (5); HRMS (ESI): m / z: calculated for C 12 H 16 OSi: 204.0970 Found: 204.0970 The data obtained correspond to those of the literature (SE Denmark, S. M. Yang, Org. Lett., 2001, 3, 1749-1752).
Analog hergestellt als farbloses Öl. H NMR (400 MHz, CDCI3): δ = 7.43-7.41 (m, 1 H), 7.37-7.35 (m, 1 H), 7.30-7.24 (m, 4H), 7.23-7.10 (m, 3H), 6.32 (s, 1 H), 4.06 ppm (s,
2H);13C NMR (100 MHz, CDCI3): δ = 157.9, 155.1 , 137.4, 129.1 , 128.8, 126.9, 123.6, 122.7, 120.5, 111.1 , 103.5, 35.1 ppm; IR (Film, cm-1): 3029, 2906, 1738, 1585, 1495, 1453, 1251 , 1163, 952, 791 , 739, 701 ; MS (El) m/z (%): 208 [M+] (100), 189 (4), 178 (14), 165 (3), 152 (3), 131 (32), 115 (3), 104 (4), 89 (7), 77 (5), 51 (3); HRMS (ESI): m/z: berechnet für C15H120: 208.0888; gefunden: 208.0888. Die erhaltenen Daten entsprechen jenen der Literatur (O. Fujimura, G. C. Fu, R. H. Grubbs J. Org. Chem. 1994, 59, 4029- 4031). Analogously prepared as a colorless oil. H NMR (400 MHz, CDCl 3 ): δ = 7.43-7.41 (m, 1H), 7.37-7.35 (m, 1H), 7.30-7.24 (m, 4H), 7.23-7.10 (m, 3H), 6.32 (s, 1H), 4.06 ppm (s, 2H); 13 C NMR (100 MHz, CDCl 3 ): δ = 157.9, 155.1, 137.4, 129.1, 128.8, 126.9, 123.6, 122.7, 120.5, 111.1, 103.5, 35.1 ppm; IR (Film, cm -1 ): 3029, 2906, 1738, 1585, 1495, 1453, 1251, 1163, 952, 791, 739, 701; MS (El) m / z (%): 208 [M + ] (100), 189 (4), 178 (14), 165 (3), 152 (3), 131 (32), 115 (3), 104 (4), 89 (7), 77 (5), 51 (3); HRMS (ESI): m / z: calculated for C 15 H 12 O: 208.0888; found: 208.0888. The data obtained correspond to those of the literature (O. Fujimura, GC Fu, RH Grubbs J. Org. Chem. 1994, 59, 4029-4031).
(3R, 4R)-3-Azido-4-benzyloxy-2,3,4,7-tetrahydroazepin-1-carbonsäure-iert utylester.(3R, 4R) -3-azido-4-benzyloxy-2,3,4,7-tetrahydroazepine-1-carboxylic acid ethyl ester.
Eine Lösung von Mo(CHCMe2Ph)(NAr)(OCMe(CF3)2)2(phen) (8 mg, 9 μιτιοΙ, 5 mol%) und A solution of Mo (CHCMe 2 Ph) (NAr) (OCMe (CF 3 ) 2 ) 2 (phen) (8 mg, 9 μιτιοΙ, 5 mol%) and
ZnCI2 (1.2 mg, 9 μιηοΙ) in CH2CI2 (18 mL) wird für 30 min auf 100°C erhitzt. Anschließend wird (2R,3R)-Allyl-(2-azido-3-benzyloxy-pent-4-enyl)-carbaminsäure-fert-butylester (66 mg, 0.177 mmol) zugegeben und das Gemisch für 30 min zum Rückfluss erhitzt. Nach Entfernen des Lösungsmittels wird der Rückstand säulenchromatographisch an Kieselgel (Hexan/Ethylacetat, 20:1) gereinigt. 1H NMR (300 MHz, CD2CI2): δ = 7.40-7.29 (m, 5H), 5.76 (br s, 2H), 4.67 (d, J = 1 1.5 Hz, 1 H), 4.55 (d, J = 11.5 Hz, 1 H), 427-3.97 (m, 2H), 3.85-3.54 (m, 4H), 1.45 (s, 9H); 13C NMR (75 MHz, CD2CI2): δ = 155.1 , 138.3, 131.1 , 129.8, 128.7, 128.3, 128.1 , 80.5, 79.1 , 72.3, 64.0, 48.8, 47.5, 28.4; [a]20 D= -26.3 (2.65, CH2CI2); IR (Film, cm"1): 3065, 3031 , 2976, 2927, 2857, 2108, 1699, 1657, 1496, 1456, 1393, 1366, 1248, 1168, 1135, 1095, 737, 698 cm"1; MS (El) m/z: 344 ([M+], < 1 ), 260 (1 ), 225 (2),186 (1),180 (3), 169 (14), 160 (6), 125 (11), 91 (100), 57 (57); HRMS (ESI) (C18H24N403+ H) berechnet: 345.1927, gefunden: 345.1921 ; C18H24N403 (344.41) berechnet: C 62.77, H 7.02, N 16.27, gefunden: C 62.72, H 6.94, N 16.19. Die erhaltenen Daten entsprechen jenen der Literatur (A. Fürstner, O. R Thiel, J. Org. Chem. 2000, 65, 1738) ZnCl 2 (1.2 mg, 9 μιηοΙ) in CH 2 Cl 2 (18 mL) is heated to 100 ° C for 30 min. Subsequently, (2R, 3R) -allyl- (2-azido-3-benzyloxy-pent-4-enyl) -carbamic acid-fert-butyl ester (66 mg, 0.177 mmol) is added and the mixture is heated to reflux for 30 min. After removal of the solvent, the residue is purified by column chromatography on silica gel (hexane / ethyl acetate, 20: 1). 1 H NMR (300 MHz, CD 2 CI 2 ): δ = 7.40-7.29 (m, 5H), 5.76 (br s, 2H), 4.67 (d, J = 1 1.5 Hz, 1 H), 4.55 (d, J = 11.5Hz, 1H), 427-3.97 (m, 2H), 3.85-3.54 (m, 4H), 1.45 (s, 9H); 13 C NMR (75 MHz, CD 2 Cl 2 ): δ = 155.1, 138.3, 131.1, 129.8, 128.7, 128.3, 128.1, 80.5, 79.1, 72.3, 64.0, 48.8, 47.5, 28.4; [a] 20 D = -26.3 (2.65, CH 2 Cl 2 ); IR (film, cm -1 ): 3065, 3031, 2976, 2927, 2857, 2108, 1699, 1657, 1496, 1456, 1393, 1366, 1248, 1168, 1135, 1095, 737, 698 cm -1 ; MS (El) m / z: 344 ([M + ], <1), 260 (1), 225 (2), 186 (1), 180 (3), 169 (14), 160 (6), 125 (11), 91 (100), 57 (57); HRMS (ESI) (C 18 H 24 N 4 0 3 + H) calculated: 345.1927, found: 345.1921; C 18 H 24 N 4 0 3 (344.41) calculated: C 62.77, H 7.02 N 16:27, found: C 62.72, H 6.94, N 16:19. The data obtained correspond to those of the literature (A. Fürstner, O. R Thiel, J. Org. Chem. 2000, 65, 1738)
Kinetische Resolution unter Verwendung von [Mo(CHCMe2Ph)(NAr)((R)-(+)- fBu2Me4(biphen))(bipy)] in Gegenwart von ZnCI2 (Ar = 2,6-diisopropylphenyl). Eine Lösung von [Mo(CHCMe2Ph)(NAr)((R)-(+)-fBu2Me4(biphen))(bipy)] (31 mg, 33 μιτιοΙ, 5 mol%) und ZnCI2 (4.5 mg, 33 μιτιοΙ) in Toluol (2.6 mL) wurde 30 min bei 80°C gerührt. Nach dieser Aktivierungsphase wurde das Gemisch auf Raumtemperatur abgekühlt und eine Lösung von (6E)-6-Methyl-5-fert-butyldimethylsiloxy-1 ,6-oktadien (168 mg, 660 μιτιοΙ)
in Toluol (4 mL) zugegeben. Das Gemisch wurde im geschlossenen Gefäß 80 min gerührt bevor die Umsetzung durch Zugabe von MeOH (3 mL) abgebrochen wurde. Das Gemisch wurde eingeengt und der bräune Rückstand chromatographisch gereinigt. Die erhaltenen Produkte haben folgende spektroskopische Eigenschaften:Kinetic resolution using [Mo (CHC Me 2 Ph) (NAr) ((R) - (+) - f Bu 2 Me 4 (biphene) (bipy)] in the presence of ZnCl 2 (Ar = 2,6-diisopropylphenyl) , A solution of [Mo (CHCMe 2 Ph) (NAr) ((R) - (+) - fBu 2 Me 4 (biphene) (bipy)] (31 mg, 33 μιτιοΙ, 5 mol%) and ZnCl 2 (4.5 mg, 33 μιτιοΙ) in toluene (2.6 mL) was stirred at 80 ° C for 30 min. After this activation phase, the mixture was cooled to room temperature and a solution of (6E) -6-methyl-5-tert-butyldimethylsiloxy-1,6-octadiene (168 mg, 660 μιτιοΙ) in toluene (4 mL). The mixture was stirred in a closed vessel for 80 minutes before the reaction was stopped by addition of MeOH (3 mL). The mixture was concentrated and the brown residue was purified by chromatography. The products obtained have the following spectroscopic properties:
(6£)-6-Methyl-5-fert-butyldimethylsiloxy-1,6-oktadien. -6-methyl-5-tert-butyldimethylsiloxy-1,6-octadiene. (6 £)
ee = 90% (bestimmt durch GC an chiraler Phase: lvadex-1/PS086 (Dimethyl-pentyl-ß- cyclodextrin, 25 m)); 1H NMR (400 MHz, CDCI3): δ = 5.87-5.77 (m, 1 H), 5.38-5.32 (m, 1 H), 5.02-4.91 (m, 2H), 3.95 (t, J = 7.1 Hz, 1 H), 2.10-1.91 (m, 2H), 1.66-1.44 (m, 8H), 0.87 (s, 9H), 0.02 (s, 3H), -0.03 (s, 3H); 13C NMR (100 MHz, CDCI3): δ = 139.1 , 138.4, 119.8, 114.3, 78.2, 35.7, 30.3, 26.0, 18.4, 13.1 , 10.9, -4.5, -4.8; IR (Film, cm"1): 2929, 2858, 1738, 1641 , 1472, 1361 , 1252, 1217, 1071, 909, 833, 772, 665; MS (El) m/z (%): 254 [M+] (1); 239 (2), 197 (64), 155 (8), 141 (3), 127 (4), 75 (100), 67 (3), 59 (4), 41 (7); HRMS (ESI): m/z: berechnet für C15H3oOSi + H: 255.2144; gefunden: 255.2144. ee = 90% (determined by GC on chiral phase: lvadex-1 / PS086 (dimethylpentyl-β-cyclodextrin, 25 m)); 1 H NMR (400 MHz, CDCl 3 ): δ = 5.87-5.77 (m, 1H), 5.38-5.32 (m, 1H), 5.02-4.91 (m, 2H), 3.95 (t, J = 7.1 Hz , 1H), 2.10-1.91 (m, 2H), 1.66-1.44 (m, 8H), 0.87 (s, 9H), 0.02 (s, 3H), -0.03 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 139.1, 138.4, 119.8, 114.3, 78.2, 35.7, 30.3, 26.0, 18.4, 13.1, 10.9, -4.5, -4.8; IR (film, cm -1 ): 2929, 2858, 1738, 1641, 1472, 1361, 1252, 1217, 1071, 909, 833, 772, 665; MS (El) m / z (%): 254 [M + ] (1); 239 (2), 197 (64), 155 (8), 141 (3), 127 (4), 75 (100), 67 (3), 59 (4), 41 (7); HRMS (ESI): m / z: calculated for C 15 H 3 oOSi + H: 255.2144; found: 255.2144.
2-Methyl-1-tert-butyldimethylsiloxy-2-cyclopenten.2-methyl-1-tert-butyldimethylsilyloxy-2-cyclopentene.
S
ee = 60% (bestimmt durch GC an chiraler Phase: BGB-176/SE-52 (2,3-Dimethyl-6-fert- butyldimethylsilyl-ß-cyclodextrin, 30 m)); H NMR (400 MHz, CDCI3): δ = 5.47-5.45 (m, 1 H), 4.66-4.63 (m, 1 H), 2.40-2.32 (m, 1 H), 2.28-2.20 (m, 1 H), 2.18-2.10 (m, 1 H), 1.71 (s, 3H), 1.70-1.63 (m, 1 H), 0.92 (s, 9H), 0.10 (s, 3H), 0.09 (s, 3H); 13C NMR (100 MHz, CDCI3): δ = 142.2, 126.9, 80.3, 34.5, 29.8, 26.1 , 14.0, -4.3, -4.6; IR (Film, cm 1): 2930, 2856, 1462, 1354, 1249, 1080, 992, 884, 833, 772, 669; MS (El) m/z (%): 212 [M+] (9), 197 (2), 137 (3), 155 (32), 75 (100), 59 (3); HRMS (ESI): m/z: berechnet für C12H24OSi: 212.1596; gefunden: 212.1596.
S ee = 60% (determined by GC on chiral phase: BGB-176 / SE-52 (2,3-dimethyl-6-tert-butyldimethylsilyl-β-cyclodextrin, 30 m)); H NMR (400 MHz, CDCl 3 ): δ = 5.47-5.45 (m, 1H), 4.66-4.63 (m, 1H), 2.40-2.32 (m, 1H), 2.28-2.20 (m, 1H ), 2.18-2.10 (m, 1H), 1.71 (s, 3H), 1.70-1.63 (m, 1H), 0.92 (s, 9H), 0.10 (s, 3H), 0.09 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ): δ = 142.2, 126.9, 80.3, 34.5, 29.8, 26.1, 14.0, -4.3, -4.6; IR (film, cm 1 ): 2930, 2856, 1462, 1354, 1249, 1080, 992, 884, 833, 772, 669; MS (El) m / z (%): 212 [M + ] (9), 197 (2), 137 (3), 155 (32), 75 (100), 59 (3); HRMS (ESI): m / z: calculated for C 12 H 24 OSi: 212.1596; found: 212.1596.
Claims
Patentansprüche claims
1 Metallorganische Verbindungen der allgemeinen Formel I 1 organometallic compounds of general formula I.
in der in the
M für Mo oder W steht, M stands for Mo or W,
R für Ci-Ci2-Alkyl, 5- bis 18-glied riges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12- Alkyloxy, Di(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro-Resten substituiert sein können, steht, R is Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn by one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, C 1 -C 12 -, alkyloxy Di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
die Substituenten X, Y gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: Halogen, Methansulfonyloxy, Trifluormethansulfonyloxy, Benzolsulfonyloxy, Toluolsulfonyloxy, Pyrrolyl, C1-C12- Alkyloxy, 5- bis 18-gliedriges Aryloxy, Tri(C Ci2-Alkyl)silyloxy, Di(CrCi2-Alkyl)(C6-the substituents X, Y may be identical or different and may be selected independently of one another from halogen, methanesulphonyloxy, trifluoromethanesulphonyloxy, benzenesulphonyloxy, toluenesulphonyloxy, pyrrolyl, C 1 -C 12 -alkyloxy, 5- to 18-membered aryloxy, tri (C Ci 2- alkyl) silyloxy, di (C 1 -C 2 -alkyl) (C 6 -
Ci8-Aryl)silyloxy, (Ci-Ci2-Alkyl)di(C6-Ci8-Aryl)silyloxy, Tris(Ci-Ci2-Alkyloxy)silyloxy, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkoxy, Di-(CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, , Ci 8 -aryl) silyloxy, (Ci-Ci 2 -alkyl) di (C 6 -C 8 -aryl) silyloxy, tris (Ci-Ci 2 -Alkyloxy) silyloxy, which in turn with one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, Ci-C 2 alkoxy, di (CrC 4 alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
R2 für H, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di(CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, steht, R 2 is H, Ci-Ci 2 alkyl, 5- to 18-membered aryl, which in turn with one or more identical or different Ci-Ci 2 alkyl, 5- to 18-membered aryl, C 1 -C 2 alkyloxy , Di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
R3 für Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12-R 3 is Ci-Ci 2 -alkyl, 5- to 18-membered aryl, which in turn by one or more identical or different Ci-Ci 2 -alkyl, 5- to 18-membered aryl, C 1 -C 12 -
Alkyloxy, Di(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, steht, Alkyloxy, di (Ci-C 4 alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted,
Ra, Rb, Rc, Rd, Re, Rf, R9, Rh gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d-R a , R b , R c , R d , R e , R f , R 9 , R h may be the same or different and may be selected independently from H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci 2 - alkoxycarbonyl, Ci-Ci 2 -alkyl, 5- to 18-membered aryl, d-
Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, die ihrerseits mit einem oder mehreren
gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C1-C12- Alkyloxy, Di-(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können, oder die Reste Rd und Re unter Bildung eines 5 bis 8 gliedrigen Ringes mit einander verbunden sind. Ci 2 alkyloxy, di- (Ci-C 4 alkyl) amino, which in turn with one or more identical or different Ci-Ci2-alkyl, 5- to 18-membered aryl, C1-C12-alkyloxy, di- (Ci-C4-alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted, or the radicals R d and R e are joined together to form a 5 to 8 membered ring.
Metallkomplexe nach Anspruch 1 , dadurch gekennzeichnet, dass Rd und Re jeweils für einen Rest R48 stehen, der CR49R50, CR5 =CR52, CR^R^-CR^R56, CR57R58-CR59R60-CR6 R62 CR62R63=CR64R65R67 CR69R70-CR7 R72-CR73R74- CR75CR76, CR77=CR78-CR79R80-CR8 CR82 und/oder CR83R84-CR85=CR87-CR88CR89 bedeutet, in welchem R49, R50, R5 , R52, R53, R54, R55, R56, R57, R58, R59, R60, R6 , p62 p63 p64 p65 p66 p67 p68 p69 p70 p71 p72 p73 p74 p75 p76 p77 p78 p79Metal complexes according to claim 1, characterized in that R d and R e each represent a radical R 48 which is CR 49 R 50 , CR 5 = CR 52 , CR 1 R 4 -CR 2 R 56 , CR 57 R 58 -CR 59 R 60 -CR 6 R 62 CR 62 R 63 = CR 64 R 65 R 67 CR 69 R 70 -CR 7 R 72 -CR 73 R 74 -CR 75 CR 76 , CR 77 = CR 78 -CR 79 R 80 - CR 8 CR 82 and / or CR 83 R 84 -CR 85 = CR 87 -CR 88 CR 89 means in which R 49 , R 50 , R 5 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 6 , p62 p63 p64 p65 p66 p67 p68 p69 p70 p71 p72 p73 p74 p75 p76 p77 p78 p79
R80, R8 , R82, R83, R84, R85, R86, R87, R88 und R89 jeweils unabhängig voneinander ausgewählt sind und die gleiche Bedeutung haben können wie Ra. R 80 , R 8 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently selected and may have the same meaning as R a .
Metallorganische Verbindungen nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 2 darstellen: Organometallic compounds according to claim 1 or claim 2, characterized in that they represent compounds of general formula 2:
R4, R5, R6, R7, R8, R9, R 0, R gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d-Ci2-Alkyloxy, Di-(CrC4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R may be identical or different and may be selected independently of one another from H, halogen, nitro, cyano, trifluoromethyl, C 1 -C 12 -alkoxycarbonyl, Ci-Ci2-alkyl, 5- to 18-membered aryl, d-Ci2-alkyloxy, di (CrC4-alkyl) amino, which in turn with one or more identical or different Ci-Ci2-alkyl, 5- to 18-membered aryl, d-Ci2 alkyloxy, di- (Ci-C4 alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
4. Metallorganische Verbindungen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 9 darstellen:
4. organometallic compounds according to one of claims 1 to 3, characterized in that they represent compounds of general formula 9:
worin wherein
M, R1 , R2, R3 und R4, R5, R6, R7, R8, R9, R 0, R wie oben definiert sind, M, R 1 , R 2 , R 3 and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 , R are as defined above,
R27, R28, R29, R30, R3 , R32, R33, R34 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, C1-C12 Alkoxycarbonyl, C1-C12 Alkyl, 5- bis 18-gliedriges Aryl, d-Ci2-Alkyloxy, Di-(CrC4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. R 27 , R 28 , R 29 , R 30 , R 3 , R 32 , R 33 , R 34 may be the same or different and may be independently selected from: H, halogen, nitro, cyano, trifluoromethyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkyl, 5- to 18-membered aryl, d-Ci2 alkyloxy, di- (CrC 4 alkyl) amino, in turn, with one or more identical or different Ci-Ci 2 alkyl , 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
5. Metallorganische Verbindungen nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 10 darstellen: 5. organometallic compounds according to any one of claims 1 to 4, characterized in that they represent compounds of general formula 10:
worin wherein
M, R1 , R2, R3, R4, R5, R6, R7, R8, R9, R 0 und R wie in den Ansprüchen 1 und 3 definiert sind und M, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 0 and R are as defined in claims 1 and 3 and
R35, R36, R37, R38 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(d-C4- Alkyl)amino, Tri(Ci-Ci2-Alkyl)silyl, Di(Ci-Ci2-Alkyl)(C6-Ci8-Aryl)silyl, (C1-C12-
Alkyl)di(C6-Ci8-Aryl)silyl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen d-C^-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(C-|-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können.
Metallorganische Verbindungen nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 17 darstellen: R 35 , R 36 , R 37 , R 38 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci 2 alkyl, 5- to 18-membered aryl, Ci -C 2 alkyloxy, di- (dC 4 - alkyl) amino, tri (Ci-Ci 2 -alkyl) silyl, di (Ci-Ci 2 alkyl) (C 6 -C 8 aryl) silyl, (C 1 -C 12 - Alkyl) di (C 6 -C 8 -aryl) silyl, which in turn with one or more identical or different dC ^ alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy, di (C- | -C4 - Alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted. Organometallic compounds according to Claim 1 or Claim 2, characterized in that they represent compounds of the general formula 17:
in der R , R2, R3, X und Y wie in Anspruch 1 definiert sind und in which R, R 2 , R 3 , X and Y are as defined in claim 1 and
R40, R4 , R42, R43, R44, R45, R46, R47 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di-(CrC4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 may be the same or different and may be independently selected from H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci2-alkoxycarbonyl , Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy, di- (Ci-C4-alkyl) amino, which in turn with one or more identical or different Ci-Ci2-alkyl, 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di- (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
7. Metallorganische Verbindungen nach einem der Ansprüche 1 , 2 oder 4, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 24 darstellen: 7. organometallic compounds according to any one of claims 1, 2 or 4, characterized in that they represent compounds of general formula 24:
worin
M, R1 , R2 und R3 sowie R40, R4 , R42, R43, R44, R45, R46 und R47 wie in den Ansprüchen 1 und 4 definiert sind und wherein M, R 1 , R 2 and R 3 and R 40 , R 4 , R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are as defined in claims 1 and 4 and
R27, R28, R29, R30, R3 , R32, R33, R34 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, Ci-Ci2-Alkoxycarbonyl, Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen Ci-Ci2-Alkyl, 5- bis 18-gliedriges Aryl, d- Ci2-Alkyloxy, Di-(Ci-C4-Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. R 27 , R 28 , R 29 , R 30 , R 3 , R 32 , R 33 , R 34 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci2- Alkoxycarbonyl, Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy, di- (Ci-C4-alkyl) amino, which in turn with one or more identical or different Ci-Ci2-alkyl, 5- to 18-membered aryl, d- Ci2 alkyloxy, di- (Ci-C4 alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
8. Metallorganische Verbindungen nach einem der Ansprüche 1 , 2, 4 oder 7, dadurch gekennzeichnet, dass sie Verbindungen der allgemeinen Formel 25 darstellen: 8. organometallic compounds according to any one of claims 1, 2, 4 or 7, characterized in that they represent compounds of general formula 25:
worin wherein
M, R1 , R2 und R3 sowie R40, R4 , R42, R43, R44, R45, R46 und R47 wie in den Ansprüchen 1 und 4 definiert sind und M, R 1 , R 2 and R 3 and R 40 , R 4, R 42 , R 43 , R 44 , R 45 , R 46 and R 47 are as defined in claims 1 and 4 and
R35, R36, R37, R38 gleich oder verschieden sein können und unabhängig voneinander ausgewählt werden können aus: H, Halogen, Nitro, Cyano, Trifluormethyl, C Ci2-Alkyl, 5- bis 18-gliedriges Aryl, C Ci2-Alkyloxy, Di-(C C4- Alkyl)amino, Tri(Ci-Ci2-Alkyl)silyl, Di(Ci-Ci2-Alkyl)(C6-Ci8-Aryl)silyl, (C1-C12- Alkyl)di(C6-Ci8-Aryl)silyl, die ihrerseits mit einem oder mehreren gleichen oder verschiedenen CrCi2-Alkyl, 5- bis 18-gliedriges Aryl, Ci-Ci2-Alkyloxy, Di-(d-C4- Alkyl)amino, Halogen, Trifluormethyl, Cyano, Nitro Resten substituiert sein können. R 35 , R 36 , R 37 , R 38 may be identical or different and may be selected independently of one another from: H, halogen, nitro, cyano, trifluoromethyl, C 2- C 2 -alkyl, 5- to 18-membered aryl, C is Ci 2 alkyloxy, di- (CC 4 - alkyl) amino, tri (Ci-Ci 2 -alkyl) silyl, di (Ci-Ci 2 alkyl) (C 6 -C 8 aryl) silyl, (C1-C12 Alkyl) di (C 6 -C 8 -aryl) silyl, which in turn contains one or more identical or different C 1 -C 12 -alkyl, 5- to 18-membered aryl, C 1 -C 12 -alkyloxy, di (C 1 -C 4 -alkyl) amino, halogen, trifluoromethyl, cyano, nitro radicals may be substituted.
9. Verfahren zur Herstellung der Metallkomplexe mit der allgemeinen Formel I
9. A process for the preparation of the metal complexes having the general formula I.
worin M, X, Y, R1 , R2, R3, Ra, Rb, Rc, Rd, Re, Rf, R9, Rh wie in Anspruch 1 definiert sind, wherein M, X, Y, R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , R f , R 9 , R h are as defined in claim 1,
bei dem eine Verbindung where a connection
worin M, X, Y, R-ι , R2, R3 wie in Anspruch 1 definiert sind, wherein M, X, Y, R 1, R 2 , R 3 are as defined in claim 1,
mit einer Verbindung der allgemeinen Formel II with a compound of general formula II
worin Ra, Rb, Rc, Rd, Re, Rf, R9, Rh wie in Anspruch 1 definiert sind, wherein R a , R b , R c , R d , R e , R f , R 9 , R h are as defined in claim 1,
umgesetzt wird. is implemented.
Verwendung der Verbindungen mit der allgemeinen Formel I Use of the compounds of the general formula I
worin M, X, Y, R1 , R2, R3, Ra, Rb, Rc, Rd, Re, Rf, R9, Rh wie in Anspruch 1 definiert sind, als Präkatalysatoren für Olefinmetathese-Reaktionen.
wherein M, X, Y, R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , R f , R 9 , R h are as defined in claim 1 as precatalysts for olefin metathesis reactions.
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US10427146B2 (en) | 2013-10-01 | 2019-10-01 | Ximo Ag | Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis |
WO2021239891A1 (en) | 2020-05-27 | 2021-12-02 | Verbio Vereinigte Bioenergie Ag | Air-stable imido alkylidene complexes and use thereof in olefin metathesis reactions |
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US10343153B2 (en) | 2013-03-14 | 2019-07-09 | Ximo Ag | Metathesis catalysts and reactions using the catalysts |
US11285466B2 (en) | 2013-03-14 | 2022-03-29 | Verbio Vereinigte Bioenergie Ag | Metathesis catalysts and reactions using the catalysts |
US10427146B2 (en) | 2013-10-01 | 2019-10-01 | Ximo Ag | Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis |
WO2021239891A1 (en) | 2020-05-27 | 2021-12-02 | Verbio Vereinigte Bioenergie Ag | Air-stable imido alkylidene complexes and use thereof in olefin metathesis reactions |
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